WO2008047592A1 - Aqueous coating agent - Google Patents

Aqueous coating agent Download PDF

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Publication number
WO2008047592A1
WO2008047592A1 PCT/JP2007/069199 JP2007069199W WO2008047592A1 WO 2008047592 A1 WO2008047592 A1 WO 2008047592A1 JP 2007069199 W JP2007069199 W JP 2007069199W WO 2008047592 A1 WO2008047592 A1 WO 2008047592A1
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WO
WIPO (PCT)
Prior art keywords
aqueous coating
coating agent
pigment
copolymer
pigment ink
Prior art date
Application number
PCT/JP2007/069199
Other languages
French (fr)
Japanese (ja)
Inventor
Shinya Kanbe
Takayuki Maki
Yousuke Asai
Morikatsu Matsunaga
Yoshio Mori
Original Assignee
Toagosei Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Priority to US12/441,727 priority Critical patent/US20100068386A1/en
Priority to JP2008539737A priority patent/JP4780196B2/en
Priority to CN2007800347481A priority patent/CN101516632B/en
Priority to KR1020097004109A priority patent/KR101385824B1/en
Priority to EP20070828939 priority patent/EP2075138B1/en
Publication of WO2008047592A1 publication Critical patent/WO2008047592A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0054—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
    • C09D155/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

  • the present invention relates to an aqueous coating agent excellent in scratch resistance, water resistance, gloss imparting effect and ink jet discharge suitability, and an aqueous coating liquid containing the coating agent.
  • the ink jet (recording) method is a recording method in which characters and images are obtained by ejecting ink from fine nozzles and attaching them to the surface of a recording medium.
  • Inkjet inks can be broadly classified into dye inks and pigment inks.
  • pigment inks having excellent weather resistance and water resistance of printed matter such as printed matter have been widely used.
  • a method of coating the surface of an inkjet recording with a protective layer has been proposed.
  • the method for forming the protective layer include a film laminating method in which a transparent film is laminated (Patent Document 1), a liquid laminating method in which a resin solution is applied to form a film on the surface of a recorded material (Patent Documents 2 and 3), etc.
  • Patent Document 1 a film laminating method in which a transparent film is laminated
  • Patent Documents 2 and 3 a liquid laminating method in which a resin solution is applied to form a film on the surface of a recorded material
  • the inkjet discharge suitability means that the discharge liquid is used for a long time in the inkjet system. ⁇ Ensure that the discharge speed and direction are stable and that problems such as nozzle clogging do not occur.
  • Patent Document 6 As a method other than surface coating, a method of adding a silicone polymer exhibiting lubricity as an additive to pigment ink has been proposed (Patent Document 6).
  • Patent Document 6 since the silicone polymer used in Patent Document 6 has a high molecular weight, adding an amount of an additive capable of imparting sufficient scratch resistance deteriorates the dispersion of the pigment and causes aggregation or increases the pigment ink. There were problems such as stickiness and poor ink jetting suitability.
  • Patent Document 1 JP-A-9 70960 (Claims)
  • Patent Document 2 JP-A-9 48180 (Claims)
  • Patent Document 3 JP-A-9 262971 (Claims)
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-39006 (Claims)
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-50751 (Claims)
  • Patent Document 6 Special Table 2000-506198 (Claims)
  • the present invention includes an aqueous coating agent that can be applied to a recording medium by an ink jet method and can form a film having excellent scratch resistance, water resistance, and gloss on the image surface, and the coating agent.
  • An aqueous coating solution is provided.
  • the main first invention of the present invention has an aqueous coating agent strength S applied to a recording medium by an ink jet method, a silicone side chain, and an ethylenically unsaturated carboxylic acid-containing monomer is essential in the main chain.
  • This is a water-based coating agent for pigment ink jet.
  • the main second invention is the ink jet method, wherein the graft copolymer is filled in a tank different from the pigment ink, discharged from a different nozzle, and applied to a recorded matter.
  • Water-based coating for pigment ink jet containing a water-based coating agent.
  • acrylic acid or methacrylic acid is represented as (meth) acrylic acid
  • acrylate or methacrylate is represented as (meth) acrylate.
  • the aqueous coating agent of the present invention By applying the aqueous coating agent of the present invention to a pigment ink, a pigment ink recorded matter having sufficient scratch resistance, water resistance and gloss can be obtained in an ink jet system.
  • the present coating agent can perform stable inkjet ejection over a long period of time when used as an additive having high inkjet ejection suitability.
  • the coating agent of the present invention can be used as an aqueous coating liquid without being mixed with the pigment ink.
  • the aqueous coating agent of the present invention contains a graft copolymer described in detail below as an essential component.
  • the graft copolymer has a silicone-based side chain, and the main chain contains an ethylenically unsaturated carboxylic acid-containing monomer as an essential component, and optionally contains other copolymerizable monomers as acid components. Is 40 to 200 mg—KOH / g (solid content) and the weight average molecular weight is 5
  • the structural unit of the silicone side chain that constitutes the graft copolymer includes dimethylsiloxane, alkyl-modified siloxane, alkylene oxide-modified siloxane, and phenyl-modified siloxane. From the viewpoint of properties, a silicone-based side chain of a dimethylsiloxane unit is preferable.
  • Examples of a method for introducing a silicone side chain into the graft copolymer include a method using a radical polymerizable silicone macromonomer and a method using a polymer reaction.
  • the method using a silicone macromonomer is useful in terms of the ease of the production process and economy.
  • the silicone macromonomer is not particularly limited.
  • a living polymer is obtained by anionic polymerization of cyclic siloxane using lithium trialkylsilanolate as an initiator, and this is reacted with ⁇ -methacryloxypropyldimethylmonochlorosilane.
  • a method of condensing a terminal silanol group-containing silicone with an organic silicon compound such as ⁇ -metataloxypropyldimethylmonochlorosilane Japanese Patent Publication No. 60-123518.
  • the silicone macromonomer is particularly preferably one in which (meth) acrylate is introduced at one end. Further, from the viewpoint of chemical stability, it is preferable that one end of the (meth) ate silyl silicone macromonomer at one end is an alkylsilyl end, a hydroxy group, an epoxy group, an amino group, an alkoxy group. It is not desirable for active substituents such as Examples of these commercial products include “ ⁇ -5”, “ ⁇ -30”, “ ⁇ -32” (all trade names) manufactured by Toagosei Co., Ltd., and “ ⁇ -22-” manufactured by Shin-Etsu Chemical Co., Ltd. 174DX "," X-24 8201 ",” X-22-22426 "(all trade names).
  • the silicone macromonomer may be used alone or in combination of two or more.
  • a method for introducing a silicone side chain by a polymer reaction for example, there is a method using reactive silicone such as epoxy silicone, silanol silicone, and aminoamino. Specifically, the main chain how the carboxylic acid is reacted with one end epoxy-modified silicone introduced into, a method such as force s reacting an epoxy group and one terminal amino-modified silicone introduced in the main chain.
  • reactive silicone such as epoxy silicone, silanol silicone, and aminoamino.
  • the molecular weight of the silicone side chain is preferably in the range of 3,000-20,000 in terms of weight average molecular weight according to gel permeation chromatograph using polystyrene as a reference substance, and 3,000-15,000. It is more preferable that it is in the range.
  • the weight average molecular weight of the silicone side chain is less than 3,000, sufficient scratch resistance cannot be obtained, and when the weight average molecular weight exceeds 20,000, the ink jet discharge suitability is poor.
  • Main chain The main chain constituting the graft copolymer has an ethylenically unsaturated carboxylic acid-containing monomer as an essential component, and optionally other copolymerizable monomers as components, and is obtained by copolymerizing these monomers. Is.
  • Examples of the ethylenically unsaturated carboxylic acid-containing monomer include (meth) acrylic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, and maleic anhydride. Force S, among which (meth) acrylic acid is preferred.
  • the amount of the ethylenically unsaturated carboxylic acid-containing monomer to be introduced should be set so that the acid value of the graft copolymer is 40 to 200 mg KOH / g (solid content), 60 to 150 mg KOH / It is more preferable to set so as to be g. Copolymerization with an acid value of less than 40 mg KOH / g does not provide sufficient water solubility, and when the acid value exceeds 200 mg-KOH / g, the water resistance of the coating film becomes insufficient.
  • Other monomers include butyl aromatic monomers, sulfonic acid-containing monomers, alkyl (meth) acrylates, alicyclic (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylamide, and acetic acid butyl. N-Buylpyrrolidone, (meth) acrylonitrile, (meth) acrylic acid and the like.
  • ethylene glycol di (meth) acrylate polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol propane tri (meth) having two or more butyl groups in one molecule.
  • Crosslinkable monomers such as attalylate, di (meth) attaryloxetyl phosphate, triarylcyanurate, triarynoisocyanurate, dibutylbenzene, maleic acid diaryl ester, polyallyl saccharose and the like may also be included.
  • the butyl aromatic monomers include styrene monomers such as styrene, ⁇ -methylol styrene, ⁇ -methyl styrene, m-methyl styrene, p-methyl styrene, p-tert-butyl styrene, butyltoluene, and phenyl groups.
  • styrene monomers such as styrene, ⁇ -methylol styrene, ⁇ -methyl styrene, m-methyl styrene, p-methyl styrene, p-tert-butyl styrene, butyltoluene, and phenyl groups.
  • sulfonic acid-containing monomer examples include (meth) acrylic acid 2-ethyl sulfonate, styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, (meth) aryl sulfonic acid, and the like.
  • alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) atalinoleic acid.
  • alkyl (meth) acrylates include 2-ethylhexyl.
  • Examples of the alicyclic (meth) acrylate include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate, isobornyl (meth) acrylate. And rate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyalkyl (meth) acrylate and adamantyl (meth) acrylate.
  • the introduction amount of these hydroxyalkyl acrylates is preferably set so that the hydroxyl value of the graft copolymer is 30 mg-KOH / g or less, and preferably 10 mg-KOH / g or less. Is more preferable.
  • the hydroxyl value of the graft copolymer is more than 30 mg—K OH, the viscosity of the liquid containing the graft copolymer becomes high, and the ink jet discharge suitability is poor.
  • the design glass transition temperature (Tg) obtained from the following formula (1) is preferably in the range of 10 to 100 ° C, and preferably 20 to 80 ° C. More preferably, it is in the range, and particularly preferably in the range of 50 to 80 ° C.
  • the glass transition temperature of the main chain is lower than 10 ° C, the coating agent containing the graft copolymer cannot provide sufficient scratch resistance when forming a film, and when it is higher than 100 ° C, the room temperature is room temperature. It becomes difficult to form a film at this point.
  • Tg n Glass transition temperature of single polymer of n monomer (K)
  • the coating agent of the present invention contains a linear copolymer containing [1] silicone side chain and [2] main chain having the above-described constitution as an essential component but not containing a side chain. You can do it.
  • the linear copolymer not containing the side chain is [2] a monomer constituting the main chain described in the above graft copolymer. It is a copolymer composed of monomers of the same structure, and the acid value, glass transition temperature (Tg), etc., follow the above [2] main chain term.
  • Known methods for synthesizing the graft copolymer include macromonomer method, ionic polymerization method, introduction of side chain by polymer reaction, etc.
  • the macromonomer method is most suitable because it is easy to introduce an ionic functional group at the end of the chain, adjust the degree of polymerization of the main chain and side chain, and easily connect the main chain to the side chain.
  • the graft copolymer of the present invention includes a silicone macromonomer constituting a side chain together with an ethylenically unsaturated carboxylic acid-containing monomer constituting a main chain, or these In addition, it can be obtained by copolymerizing with other monomers added if desired.
  • the carboxylic acid in the copolymer must be ionized by neutralizing a part or all of it with a base.
  • bases used for neutralization include inorganic alkali agents such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and organic amines such as diethanolamine and triethanolamine. Alkali metal hydroxide is preferred!
  • the weight ratio of the segment constituting the graft side chain such as a silicone macromonomer is 10 to 80% by weight, and the corresponding monomer constituting the main chain. It is preferred that the total weight of the mer is 90 to 20% by weight, more preferably 15% to 50% by weight of the constituting graph side chain, and the corresponding total weight of monomers constituting the main chain 85 It is ⁇ 50% by weight, and most preferably, the weight ratio of the constituting graft side chain is 0 to 40% by weight, and the total weight of the monomers constituting the main chain correspondingly is 80 to 60% by weight.
  • the weight ratio of the graft side chain is less than 10% by weight, the effect of imparting lubricity will not be obtained due to the lack of silicone components, and sufficient scratch resistance will not be obtained. Since the ability to form a coating film is inferior due to the lack of the components that make up, the scratch resistance decreases.
  • the synthesis of the graft copolymer is easy because the polymerization operation and the adjustment of the molecular weight are easy, so the method using a radical polymerization initiator is preferred, and the hydrophobic monomer is difficult to dissolve in water.
  • a solution polymerization method in which polymerization is performed in a solvent is preferred.
  • Preferred solvents for radical polymerization by the solution polymerization method include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetate solvents such as ethyl acetate and butyl acetate, and aromatic solvents such as benzene, toluene and xylene.
  • radical polymerization initiator those generally used can be used, and specifically, peroxyketal, hydrated peroxide, dialkyl peroxide, disilver oxide, peroxydicarbonate. , Peroxyesters, cyano-based azobisisobutyronitrile, azobis (2-methylbutyronitrile), non-cyano-based dimethyl 2,2'-azobisisobutyrate, and the like.
  • peroxyketal hydrated peroxide
  • dialkyl peroxide dialkyl peroxide
  • disilver oxide peroxydicarbonate
  • peroxydicarbonate peroxydicarbonate
  • Peroxyesters cyano-based azobisisobutyronitrile, azobis (2-methylbutyronitrile), non-cyano-based dimethyl 2,2'-azobisisobutyrate, and the like.
  • the molecular weight is controlled quickly. Decomposition of organic peroxides and azo compounds with low temperatures is preferred, especially azo compounds.
  • the polymerization initiator is used in an amount of preferably 0.3 to 15% by weight, more preferably 0.3 to 10% by weight, based on the total weight of the polymerizable monomers.
  • mercaptoacetic acid In order to adjust the molecular weight of the graft copolymer, mercaptoacetic acid, mercaptopro An appropriate amount of a chain transfer agent such as pionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecinoremercaptan, thioglycerol may be added to the polymerization system.
  • a chain transfer agent such as pionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecinoremercaptan, thioglycerol may be added to the polymerization system.
  • the polymerization temperature is preferably 40 to 180 ° C, more preferably 50 to 150 ° C.
  • the preferred polymerization time is 3 to 25 hours.
  • the molecular weight of the graft copolymer of the present invention is in the range of 5,000 to 30,000 as a weight average molecular weight by gel permeation chromatography using polystyrene as a reference substance, and is 8,000 to 25,000. The range is more preferable, and the range of 10,000 to 20,000 is particularly preferable. If the polymer has a weight average molecular weight of less than 5,000, sufficient scratch resistance cannot be obtained, and if the weight average molecular weight exceeds 30,000, the ink jet discharge suitability is poor.
  • the aqueous coating agent of the present invention can be used with conventionally known pigment inks that are usually used.
  • the pigment ink used with the water-based coating agent of the present invention is applicable to water-based pigment inks and solvent-based pigment inks, and is not particularly limited, but is preferably used with water-based pigment inks. Masle.
  • a water-based coating agent can be used by adding to a water-based pigment ink.
  • the ink tank is filled as a water-based coating liquid, and discharged from a nozzle separate from the pigment ink. You can also In particular, the latter is more preferable because a dense film can be formed on the surface.
  • the aqueous coating solution of the present invention contains an aqueous medium as an essential component in addition to the above-mentioned 1. aqueous coating agent.
  • a mixed solvent of water and a water-soluble organic solvent is preferable from the viewpoint of preventing drying of the aqueous coating liquid and ensuring ejection stability.
  • the water is preferably ion exchange water (deionized water).
  • Water-soluble organic solvents include methyl alcohol, ethyl alcohol, ⁇ -propyl alcohol Cholesterol, isopropyl alcohol, n butyl alcohol, sec butyl alcohole, t ert Alkyl alcohols having 1 to 4 carbon atoms such as butyl alcohol, amides such as dimethylformamide, dimethylacetamide, acetone, diacetone alcohol, etc.
  • polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2- Alkylene glycols containing 2 to 6 carbon atoms, such as xanthdiol, 1, 2, 6 hexanetriol, thioglycol, hexylene glycol, diethylene glycol, and the like.
  • Lower alkyl ethers of polyhydric alcohols such as phosphorus, ethylene glycol monomethyl (or ethyl) ether, jetylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, N-methylolene 2 pyrrolidone, 2 pyrrolidone, 1 , 3 dimethyl-2 imidazolidinone and the like.
  • polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or butyl) ether are preferable.
  • said water-soluble organic solvent can be used individually or in combination of 2 or more types as needed.
  • aqueous coating liquid of the present invention as a component other than the aqueous coating agent and the aqueous medium, various known and commonly used additives that can be usually added to the aqueous pigment ink are added with a force S.
  • Such additives include surfactants, antifoaming agents, preservatives, anti-settling agents, chelating agents, thickeners, anticorrosives, antioxidants and the like.
  • Surfactants include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkylaryl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, Nonionic surfactants such as polyoxyethylene sorbitan alkyl esters, acetylene alcohol and acetylene glycol, cationic surfactants such as alkylamine salts and quaternary ammonium salts, alkylbeta And amphoteric surfactants such as alkylamine oxide.
  • the amount of the graft copolymer contained in the aqueous coating solution of the present invention is preferably in the range of 0.;! To 30% by weight, based on the total weight of the aqueous coating solution, 2 to 15% by weight. The range is more preferable.
  • the amount of the water-soluble organic solvent contained in the aqueous coating liquid is preferably in the range of 3 to 50% by weight, more preferably in the range of 5 to 40% by weight with respect to the total weight of the aqueous coating liquid.
  • the amount of water contained in the aqueous coating solution of the present invention is preferably in the range of 10 to 90% by weight, more preferably in the range of 30 to 90% by weight.
  • the pH of the aqueous coating solution is preferably in the range of 5 to 10; By setting the pH within this range, it is possible to improve the solubility of the aqueous coating agent containing the graft copolymer and improve the storage stability. In addition, corrosion of members of an apparatus to which the aqueous coating liquid is applied (for example, an ink jet recording apparatus) can be suppressed.
  • inorganic alkali agents such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic amines such as dimethylethanolamine, diethanolamine and triethanolamine are used.
  • organic acids such as citrate and tartaric acid, mineral acids such as hydrochloric acid and phosphoric acid, and the like can be used as pH adjusters.
  • the water-based coating liquid preferably has a viscosity at 25 ° C of 10 mPa's or less, more preferably 5 mPa's or less, from the viewpoint of inkjet ejection reliability.
  • the pigment used in the water-based pigment ink may be an inorganic pigment or an organic pigment! /. These can be used alone or in combination as required.
  • the dispersed particle size of the pigment is preferably 0.005 to 111 to 111, more preferably 0.05 to 5111, and most preferably 0.01 to 1111. If the dispersed particle size is 0.005 m or less, more dispersant is required to stabilize the dispersion, and the pigment itself cannot perform, and if it is 15 m or more, it is difficult to keep the dispersion state stable.
  • inorganic pigments include metal oxides such as carbon black and titanium oxide, metal sulfides, and metal chlorides.
  • Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black. Specifically, No.2300, No.900, MCF8 8, No.33, No.40, No.45, No.52, MA7, MA8, ⁇ ⁇ 2200 ⁇ (Mitsubishi Chemical Corp.
  • RAVEN1255 Coldia, product name
  • REGAL400R REGAL330R
  • REGAL66 OR MOGUL L (Cabot, product name)
  • Organic pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, Polycyclic pigments such as indolinone pigments and quinophthalone pigments; nitro pigments, nitroso pigments, and aniline black are also included.
  • azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments
  • phthalocyanine pigments such as perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments
  • Polycyclic pigments such as indolinone pigments and quinophthalone pigments
  • the organic pigment include the water-based coating agent of the present invention, and may be appropriately selected according to the type (color) of the water-based pigment ink to be obtained.
  • C ⁇ Pigment Yellow 1 C .1. Pigment Yellow 2, CI Pigment fellow «5, CI Pigment ellow 13, ui Pigment Yell ow 16, CI Pigment Yellow 74, C ⁇ Pigment Yellow 83, CI Pigment Yellow 128, etc.
  • C.LPigment Red 5 CI Pigment Red 7, CI Pigment Red 12, CI Pigment Red 48 (Ca), C.LPigment Red 48 (Mn), C.LPigment Red 57 (Ca), C.LPigment Red 11 2, Magenta pigments such as C.LPigment Red 122; C ⁇ Pigment Blue 1, C.LPigment Blue 2, C.LPigment Blue 3, C.LPigment Blue 15: 3, C.LPigment Blue 16, C.LPigment Bl and cyan pigments such as ue 22, CIVat Blue 4 and CI Vat Blue 6.
  • organic pigments such as aniline black (C ⁇ Pigment Black 1) are also included as black ink pigments. Can be mentioned.
  • a pigment dispersant is present in the aqueous pigment ink.
  • the pigment dispersant that can be used is not particularly limited, and specific examples include a cationic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a water-soluble polymer. From the viewpoint of pigment dispersion stability, a water-soluble polymer is particularly preferred.
  • water-soluble polymer examples include polyacrylic acid, polymethacrylic acid, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene (meth) acrylic acid copolymer, styrene ) Acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, and salts thereof, etc.
  • a monomer having a hydrophobic group having affinity for a pigment and a hydrophilic group Particularly preferred are copolymers with the monomers they contain.
  • These water-soluble polymers preferably have a weight average molecular weight in the range of 3,000 to 20,000 from the viewpoint of ink viscosity.
  • the content in the ink is preferably in the range of 0.;! To 15% by weight.
  • the water-based pigment ink includes the above-mentioned pigment, the pigment dispersant, and the above-mentioned 2.1 aqueous medium, 2.2 and other component powers. Agent is added. These compositions are the same as in the previous section 2.
  • the amount of the pigment dispersant contained in the ink is preferably in the range of 0.;! To 30% by weight with respect to the total weight of the ink;! To 15% by weight The range of is more preferable.
  • the amount of the pigment contained in the water-based ink is preferably in the range of 0.;! To 30% by weight; more preferably in the range of! To 15% by weight.
  • the content ratio of the pigment dispersant and the pigment contained in the water-based pigment ink is in the range of 1: 1 to 1:30 (weight ratio), preferably S, more preferably 1: 2 to 1:15. I like it!
  • the amount of the water-soluble organic solvent contained in the aqueous pigment ink is preferably 3 to 50% by weight, more preferably 3 to 40% by weight based on the total weight of the ink.
  • the amount of water contained in the aqueous pigment ink is preferably in the range of 10 to 90% by weight, and in the range of 30 to 80% by weight. More preferred.
  • the pH of the aqueous pigment ink is preferably in the range of 5 to 10; By setting the pH within this range, it is possible to improve the solubility of the coating agent and the pigment dispersant and improve the storage stability. Moreover, corrosion of members of an apparatus to which the aqueous pigment ink is applied (for example, an ink jet recording apparatus) can be suppressed.
  • an inorganic alkali agent such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an organic amine such as dimethylethanolamine, diethanolamine or triethanolamine.
  • organic acids such as citrate and tartaric acid, mineral acids such as hydrochloric acid and phosphoric acid can be used as pH adjusters.
  • a water-based pigment ink containing a water-based coating agent can be obtained by mixing and dispersing the water-based coating agent together with the components of the water-based pigment ink. Add each of the above components as they are, or add anti-drying agents and other additives as necessary, and dilute with an aqueous medium to prepare ink-jet recording inks and water-based pigment inks for writing utensils such as water-based ballpoint pens and marker pens. Can be used. In this case, in order to prevent the inkjet nozzle and the nib from becoming clogged due to drying, it is preferable to add a low-volatile or non-volatile solvent among the above water-soluble organic solvents. In order to increase the permeability to the recording medium, a volatile solvent may be added. Especially when used in water-based pigment inks for inkjet recording, it is also preferable to add a surfactant to give the ink an appropriate surface tension!
  • the ink jet recording method for discharging the aqueous pigment ink containing the aqueous coating liquid or the aqueous coating agent is not particularly limited, and a known method can be used. In particular, it is also suitable for a thermal jet method, which is generally said to have a narrow selection range of resin used due to the stability of aqueous coating agents at high temperatures and the difficulty of kogation.
  • the recording medium is not particularly limited, but the water-based coating liquid or water-based coating agent of the present invention is added to the ink jet recording paper having an ink receiving layer on the surface. It is particularly useful to apply the prepared aqueous pigment ink.
  • aqueous coating liquid of the present invention can be performed only on a portion where the pigment ink is present or on the entire surface regardless of the presence or absence of the pigment ink, and is not particularly limited.
  • T g is calculated from the above formula (1) as a value of a main chain copolymer excluding silicone side chains or a linear copolymer.
  • ⁇ Preparation of aqueous coating solution 20 parts of an aqueous solution of the above copolymer El (solid content 25%), 5 parts of glycerin, 15 parts of diethyleneglycol monoole, 2 parts of 2 pyrrolidone and 58 parts of ion-exchanged water are mixed, and pH is 8 to 8 with jetylethanolamine; It was adjusted to 10 and filtered using a membrane filter with a pore size of 5. C ⁇ m to obtain the target aqueous coating solution E1.
  • the monomer used in the synthesis of the copolymer of Example 1 was changed to 14 g of methyl methacrylate, 38 g of butyl methacrylate, 23 g of methacrylolic acid, A25gi of silicone macromonomer, and the other operations were the same as in Example 1.
  • an aqueous solution of copolymer E2 (Mw: 13,000, acid value 150 mg—K OH / g, Tg 65 ° C.) was obtained.
  • an aqueous coating solution E2 was obtained in the same manner as in Example 1.
  • the monomer composition used in the synthesis of the copolymer of Example 1 is kept as it is, azobis 2-methylobutylnitrile (ABN-E) is changed to 2. Og, and other operations are performed in the same manner as in Example 1.
  • An aqueous solution of copolymer E3 (Mw: 22,000, acid value 100 mg—KOH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution E3 was obtained in the same manner as in Example 1.
  • the monomer used in the synthesis of the copolymer of Example 1 was changed to 34 g of methyl methacrylate, 33 g of petitenomethacrylate, 8 g of methacrylolic acid, and 25 g of silicone macromonomer, and azobis-2-methylobutylnitrile ( ABN—E) was changed to 2 ⁇ Og, and the others were operated in the same manner as in Example 1 to obtain an aqueous solution of copolymer E4 (Mw: 22,000, acid value 50 mg—KOH / g, Tg65 ° C). Got. Thereafter, an aqueous coating solution E4 was obtained in the same manner as in Example 1.
  • the monomer used for the synthesis of the copolymer of Example 1 was changed to 23 g of methyl methacrylate, 33 g of butyl methacrylate, 15 g of methacrylate, 2 g of hydroxyethenore methacrylate, and 25 g of silicone macromonomer A.
  • the other procedures were carried out in the same manner as in Example 1 to obtain an aqueous solution of a copolymer E5 (Mw: 13,000, acid value lOOmg—KOH / g, hydroxyl value 17 mg—KOH / g, Tg65 ° C.). Thereafter, the aqueous coating solution E5 was further operated in the same manner as in Example 1.
  • the monomer used for the synthesis of the copolymer of Example 1 was a methyl methacrylate 25 g, a methyl methacrylate 35 g, a methacrylic acid 15 g, and a one-terminal methacryloyl-modified polydimethylsiloxane (silicone macromolecule) having a weight average molecular weight of 12,000.
  • Monomer B) was changed to 25 g, and the others were operated in the same manner as in Example 1 to obtain an aqueous solution of copolymer E6 (Mw: 15,000, acid value lOOmg—KOH / g, Tg 65 ° C.). Thereafter, an aqueous coating solution E6 was obtained in the same manner as in Example 1.
  • the monomer used for the synthesis of the copolymer of Example 1 was changed to 10 g of methyl methacrylate, 25 g of butyl methacrylate, 15 g of methacrylolic acid, and 50 g of silicone macromonomer, and the other operations were the same as in Example 1.
  • an aqueous solution of a copolymer E8 (Mw: 13,000, acid value lOOmg—K OH / g, Tg 65 ° C.) was obtained.
  • an aqueous coating solution E7 was obtained in the same manner as in Example 1.
  • the monomer used in the synthesis of the copolymer of Example 1 was changed to 60 g of butyl methacrylate, 15 g of methacrylic acid, and 25 g of silicone macromonomer, and the other operations were performed in the same manner as in Example 1 to obtain a copolymer.
  • An aqueous solution of E8 (Mw: 12,000, acid value 100 mg—KOH / g, Tg 38 ° C.) was obtained. Thereafter, an aqueous coating solution E9 was obtained in the same manner as in Example 1.
  • Example 1 The monomers used in the synthesis of the copolymer of Example 1 were changed to 52 g of methyl methacrylate, 8 g of butyl methacrylate, 15 g of methacrylolic acid, and 25 g of silicone macromonomer, and the other operations were the same as in Example 1.
  • an aqueous solution of a copolymer E10 (Mw: 12,000, acid value lOOmg—KO H / g, TglOO ° C.) was obtained.
  • an aqueous coating solution E9 was obtained in the same manner as in Example 1.
  • the monomers used in the synthesis of the copolymer of Example 1 were changed to 40 g of methyl methacrylate, 45 g of butyl methacrylate, and 15 g of methacrylic acid, and the other operations were performed in the same manner as in Example 1. Then, an aqueous solution of copolymer CI (Mw: 13,000, acid value lOOmg KOH / g, Tg 65 ° C.) was obtained. Thereafter, the same operation as in Example 1 was further performed to obtain an aqueous coating solution C1.
  • Example 1 The monomer used in the synthesis of the copolymer of Example 1 was changed to 41 g of butyl methacrylate, 34 g of methacrylic acid, and 25 g of silicone macromonomer, and the others were operated in the same manner as in Example 1 to obtain a copolymer.
  • An aqueous solution of C2 (Mw: 14,000, acid value 220 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution C2 was obtained in the same manner as in Example 1.
  • the monomers used for the synthesis of the copolymer of Example 1 were changed to 38 g of methyl methacrylate, 32 g of butyl methacrylate, 5 g of methacrylolic acid, and 25 g of silicone macromonomer, and the other operations were the same as in Example 1.
  • An aqueous solution of copolymer C3 (Mw: 13,000, acid value 33 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, the same operation as in Example 1 was further carried out to obtain an aqueous coating film C3.
  • the monomer composition used in the synthesis of the copolymer of Example 1 was kept as it was, and azobis 2-methylobutylnitrile ( ⁇ - ⁇ ) was changed to 1.2 g, and the other operations were performed in the same manner as in Example 1.
  • An aqueous solution of copolymer C4 (Mw: 35,000, acid value 100 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, the same operation as in Example 1 was further performed to obtain an aqueous coating solution C4.
  • the monomer used for the synthesis of the copolymer of Example 1 was changed to 14 g of methyl methacrylate, 52 g of methyl methacrylate, and 34 g of methacrylic acid, and the other operations were carried out in the same manner as in Example 1 to obtain copolymer C5.
  • An aqueous solution (Mw: 13,000, acid value 220 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution C5 was obtained in the same manner as in Example 1.
  • the monomer used in the synthesis of the copolymer of Example 1 was changed to 40 g of methyl methacrylate, 45 g of methyl methacrylate, and 15 g of methacrylic acid, and 1. Og of azobis-2-methylobutylnitrile (ABN-E).
  • the others were operated in the same manner as in Example 1 to obtain an aqueous solution of a copolymer C6 (Mw: 42,000, acid value lOOmg KOH / g, Tg65 ° C). Then further In the same manner as in Example 1, an aqueous coating solution C6 was obtained.
  • the monomer used for the synthesis of the copolymer of Example 1 was changed to 35 g of methyl methacrylate, 40 g of methyl methacrylate, 15 g of methacrylic acid, and 10 g of 2-hydroxyethyl methacrylate.
  • the same operation was performed to obtain an aqueous solution of copolymer C7 (Mw: 14,000, acid value lOOmg—KOH / g, hydroxyl value 43 mg—KOH / g, Tg 65 ° C.). Thereafter, the same operation as in Example 1 was further performed to obtain an aqueous coating solution C7.
  • the monomer used in the synthesis of the copolymer of Example 1 was changed to 21 g of methyl methacrylate, 31 g of petitenomethacrylate ⁇ , 15 g of methacrylolic acid, 8 g of 2-hydroxyethylenomethacrylate ⁇ , and 25 g of silicone macromonomer A,
  • the other procedures were carried out in the same manner as in Example 1 to obtain an aqueous solution of a copolymer C8 (Mw: 12,000, acid value lOOmg—KOH / g, hydroxyl value 35 mg—KOH / g, Tg65 ° C.).
  • an aqueous coating solution C8 was obtained in the same manner as in Example 1.
  • Each water-based coating liquid and pigment ink are filled into an ink cartridge of a micro bubble jet printer (registered trademark) (PIXUS iP4200, trade name, manufactured by Canon Inc.) — 301, trade name) was printed with black pigment ink, followed by application of an aqueous coating solution by the inkjet method.
  • a micro bubble jet printer registered trademark
  • PIXUS iP4200 trade name, manufactured by Canon Inc.
  • Microbubble jet printer is a registered trademark of Canon Inc.
  • the recorded matter prepared by the above operation was dried at room temperature for 24 hours, and then the printed portion was rubbed with fingers. Changes at that time were evaluated based on the following criteria.
  • the gloss of each recorded matter was visually evaluated based on the following criteria using an aqueous coating solution as a control.
  • the aqueous coating liquids of the examples had better results than the aqueous coating liquids of the comparative examples. In other words, it was possible to form a film having good ink jet discharge suitability and excellent scratch resistance, water resistance and gloss.
  • the aqueous coating agent comprising the graft copolymer of the present invention forms a film having excellent scratch resistance, water resistance, and gloss on the surface of an ink jet recorded product, and further has good ink jet discharge suitability. It is extremely useful as a coating agent to be applied to the surface of recorded matter depending on the method.
  • a printed matter excellent in scratch resistance, water resistance and gloss can be obtained by using the coating liquid of the present invention in combination with the pigment ink. This is especially useful for applications that require clear images over a long period of time, such as outdoor posters.

Abstract

[PROBLEMS] To provide an aqueous coating agent which can be coated on a recording medium in an ink-jet mode and enables to form a film having excellent scratch resistance, water resistance and gloss on the image surface, and also provide an aqueous coating solution comprising the coating agent. [MEANS FOR SOLVING PROBLEMS] An aqueous coating agent for pigment ink-jet, comprising a graft copolymer having a silicone side chain and, as the main chain, a copolymer essentially composed of a monomer containing an ethylenically unsaturated carboxylic acid, and having an acid value of 40 to 200 mg-KOH/g (solid) and a weight average molecular weight of 5,000 to 30,000; and an aqueous coating solution for pigment ink-jet, which comprises an aqueous coating agent comprising the graft copolymer and which is intended to be charged in a tank different from one for a pigment ink in an ink-jet mode, to be ejected from a separate nozzle and to be coated on a recorded article.

Description

明 細 書  Specification
水性コーティング剤  Water-based coating agent
技術分野  Technical field
[0001] 本発明は、耐擦過性、耐水性、光沢の付与効果およびインクジェット吐出適性に優 れた水性コーティング剤、および該コーティング剤を含有する水性コーティング液に 関する。  [0001] The present invention relates to an aqueous coating agent excellent in scratch resistance, water resistance, gloss imparting effect and ink jet discharge suitability, and an aqueous coating liquid containing the coating agent.
背景技術  Background art
[0002] インクジェット（記録)方式とは微細なノズルからインクを吐出し、記録媒体の表面に 付着させることによって文字や画像を得る記録方式である。このインクジェット用インク としては大別して染料インクと顔料インクがある力 近年、印刷物などの記録物の耐 候性、耐水性に優れた顔料インクが広く使用されるようになってきている。  The ink jet (recording) method is a recording method in which characters and images are obtained by ejecting ink from fine nozzles and attaching them to the surface of a recording medium. Inkjet inks can be broadly classified into dye inks and pigment inks. In recent years, pigment inks having excellent weather resistance and water resistance of printed matter such as printed matter have been widely used.
[0003] しかしながら、顔料インクを使用した際の問題として、記録表面に顔料が残存するた めに記録物の耐擦過性や光沢が劣ることがある。特に表面にインク受容層を有する 記録媒体に顔料インクで印字を行った際には、表面に顔料が多く残り、この問題が 顕著となる。  [0003] However, as a problem when using pigment ink, there are cases where the scratch resistance and gloss of the recorded matter are inferior because the pigment remains on the recording surface. In particular, when printing with a pigment ink on a recording medium having an ink receiving layer on the surface, a large amount of pigment remains on the surface, and this problem becomes remarkable.
[0004] これらの問題を解決するために、インクジェット記録物の表面を保護層で被覆する 方法が提案されている。保護層の形成方法としては例えば透明なフィルムでラミネー トするフィルムラミネート法 (特許文献 1)、樹脂溶液を塗布して記録物表面に膜を形 成するリキッドラミネート法（特許文献 2、 3)などが提案されている。し力もながら、これ らの方法は高コストのラミネートの装置が必要となる問題がある。  [0004] In order to solve these problems, a method of coating the surface of an inkjet recording with a protective layer has been proposed. Examples of the method for forming the protective layer include a film laminating method in which a transparent film is laminated (Patent Document 1), a liquid laminating method in which a resin solution is applied to form a film on the surface of a recorded material (Patent Documents 2 and 3), etc. Has been proposed. However, these methods have a problem that an expensive laminating apparatus is required.
[0005] 近年になって、この問題を解決するために記録媒体にインクジェット記録方式で画 像形成を行った後に、同じくインクジェット記録方式でコーティング液を吐出して表面 にトップコート層を形成する方法が提案されている（特許文献 4、 5)。し力もながら、こ れらの文献に示されるコーティング液はシリコーンのような活性を示す成分が含まれ な!/、ため耐擦過性が不十分で、またエマルシヨン樹脂を使用して!/、るためインクジェ ット吐出適性も劣っていた。  [0005] In recent years, in order to solve this problem, after forming an image on a recording medium by an ink jet recording method, a method of forming a top coat layer on the surface by discharging a coating liquid by the same ink jet recording method Have been proposed (Patent Documents 4 and 5). However, the coating solutions shown in these documents do not contain silicone-like active ingredients! /, So they have insufficient scratch resistance, and use emulsion resins! Therefore, the ink jetting suitability was also inferior.
ここでインクジェット吐出適性とは、インクジェット方式において長期に亘り吐出液の 吐出速度、吐出方向が安定し、またノズルの目詰まりなどの問題を起こさないことを 曰 Here, the inkjet discharge suitability means that the discharge liquid is used for a long time in the inkjet system. 吐出 Ensure that the discharge speed and direction are stable and that problems such as nozzle clogging do not occur.
[0006] また、表面被覆以外の手法として、顔料インクへの添加剤として滑性を示すシリコー ンポリマーを添加する手法が提案されている（特許文献 6)。し力もながら、特許文献 6で使用されるシリコーンポリマーは分子量が高いため、十分な耐擦過性を付与でき る添加剤量を加えると顔料の分散が悪化して凝集が起こったり、顔料インクが増粘し てインクジェット吐出適性が悪くなる等の問題があった。  [0006] As a method other than surface coating, a method of adding a silicone polymer exhibiting lubricity as an additive to pigment ink has been proposed (Patent Document 6). However, since the silicone polymer used in Patent Document 6 has a high molecular weight, adding an amount of an additive capable of imparting sufficient scratch resistance deteriorates the dispersion of the pigment and causes aggregation or increases the pigment ink. There were problems such as stickiness and poor ink jetting suitability.
[0007] 特許文献 1：特開平 9 70960号公報（特許請求の範囲）  [0007] Patent Document 1: JP-A-9 70960 (Claims)
特許文献 2 :特開平 9 48180号公報 (特許請求の範囲）  Patent Document 2: JP-A-9 48180 (Claims)
特許文献 3 :特開平 9 262971号公報 (特許請求の範囲）  Patent Document 3: JP-A-9 262971 (Claims)
特許文献 4：特開 2001— 39006号公報（特許請求の範囲）  Patent Document 4: Japanese Patent Laid-Open No. 2001-39006 (Claims)
特許文献 5 :特開 2004— 50751号公報（特許請求の範囲）  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-50751 (Claims)
特許文献 6 :特表 2000— 506198号公報（特許請求の範囲）  Patent Document 6: Special Table 2000-506198 (Claims)
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0008] 本発明は前記背景技術に鑑み、インクジェット方式によって記録媒体に塗布され、 耐擦過性、耐水性、光沢に優れた膜を画像表面に形成し得る水性コーティング剤、 および該コーティング剤を含有する水性コーティング液を提供するものである。 In view of the above-mentioned background art, the present invention includes an aqueous coating agent that can be applied to a recording medium by an ink jet method and can form a film having excellent scratch resistance, water resistance, and gloss on the image surface, and the coating agent. An aqueous coating solution is provided.
課題を解決するための手段  Means for solving the problem
[0009] 本発明者らは、前記課題を解決するために鋭意検討した結果、シリコーン系側鎖を 有する特定なグラフト共重合体を含む水性コーティング剤により前記課題を解決でき ることを見出し、本発明を完成するに至った。 [0009] As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by using an aqueous coating agent containing a specific graft copolymer having a silicone side chain. The invention has been completed.
即ち、本発明の主要な第一の発明は、インクジェット方式によって記録媒体に塗布 される水性コーティング剤力 S、シリコーン系側鎖を有し、主鎖にはエチレン性不飽和 カルボン酸含有モノマーを必須構成成分とする共重合体からなる、酸価が 40〜200 mg KOH/g (固形分）であり、重量平均分子量が 5, 000—30, 000の範囲にあ るグラフト共重合体を含有することを特徴とする顔料インクジェット用水性コーティング 剤である。 [0010] また、主要な第二の発明は、インクジェット方式において、顔料インクとは別のタンク に充填され、別ノズルから吐出され記録物に塗布されることを特徴とする前記グラフト 共重合体を含有する水性コーティング剤を含む顔料インクジェット用水性コーティン グ：液である。 That is, the main first invention of the present invention has an aqueous coating agent strength S applied to a recording medium by an ink jet method, a silicone side chain, and an ethylenically unsaturated carboxylic acid-containing monomer is essential in the main chain. Containing a graft copolymer having an acid value of 40 to 200 mg KOH / g (solid content) and a weight average molecular weight in the range of 5,000 to 30,000, consisting of a copolymer as a constituent component This is a water-based coating agent for pigment ink jet. [0010] Further, the main second invention is the ink jet method, wherein the graft copolymer is filled in a tank different from the pigment ink, discharged from a different nozzle, and applied to a recorded matter. Water-based coating for pigment ink jet containing a water-based coating agent.
尚、本明細書においては、アクリル酸又はメタクリル酸を (メタ）アクリル酸と、アタリレ ート又はメタタリレートを (メタ）アタリレートとして表す。  In the present specification, acrylic acid or methacrylic acid is represented as (meth) acrylic acid, and acrylate or methacrylate is represented as (meth) acrylate.
発明の効果  The invention's effect
[0011] 本発明の水性コーティング剤を顔料インクに適用することで、インクジェット方式に おいて、十分な耐擦過性、耐水性、光沢を持った顔料インク記録物が得られる。また 、本コーティング剤は、インクジェット吐出適性が高ぐ添加剤として使用した際、長期 にわたつて安定なインクジェット吐出を行える。さらに、本発明のコーティング剤は顔 料インクと混合せずに水性コーティング液としても使用できる。  [0011] By applying the aqueous coating agent of the present invention to a pigment ink, a pigment ink recorded matter having sufficient scratch resistance, water resistance and gloss can be obtained in an ink jet system. In addition, the present coating agent can perform stable inkjet ejection over a long period of time when used as an additive having high inkjet ejection suitability. Furthermore, the coating agent of the present invention can be used as an aqueous coating liquid without being mixed with the pigment ink.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 1.水性コーティング剤  [0012] 1. Aqueous coating agent
本発明の水性コーティング剤は下記に詳述するグラフト共重合体を必須成分として 含有するものである。  The aqueous coating agent of the present invention contains a graft copolymer described in detail below as an essential component.
1.1 グラフト共重合体  1.1 Graft copolymer
グラフト共重合体は、シリコーン系の側鎖を有し、主鎖にはエチレン性不飽和カル ボン酸含有モノマーを必須構成成分とし、所望によりその他共重合可能なモノマーを 構成成分とする、酸価が 40〜200mg— KOH/g (固形分）で、重量平均分子量が 5 The graft copolymer has a silicone-based side chain, and the main chain contains an ethylenically unsaturated carboxylic acid-containing monomer as an essential component, and optionally contains other copolymerizable monomers as acid components. Is 40 to 200 mg—KOH / g (solid content) and the weight average molecular weight is 5
, 000—30, 000の範囲にあるグラフ卜共重合体である。 , 000-30,000, a graph 卜 copolymer in the range.
[0013] [1]シリコーン系側鎖について [0013] [1] Silicone side chain
グラフト共重合体を構成するシリコーン系側鎖の構成単位としては、ジメチルシロキ サンの他、アルキル変性シロキサン、アルキレンォキシド変性シロキサン、フエニル変 性シロキサンなどがあるが、滑性付与効果、化学的安定性の観点からジメチルシロキ サン単位のシリコーン系側鎖が好ましい。  The structural unit of the silicone side chain that constitutes the graft copolymer includes dimethylsiloxane, alkyl-modified siloxane, alkylene oxide-modified siloxane, and phenyl-modified siloxane. From the viewpoint of properties, a silicone-based side chain of a dimethylsiloxane unit is preferable.
[0014] グラフト共重合体にシリコーン系側鎖を導入する方法としては、例えばラジカル重合 性のシリコーンマクロモノマーを用いる方法や高分子反応により導入する方法等があ る力 シリコーンマクロモノマーを用いる方法が製造工程の容易さ、経済性などの点 で有用である。 [0014] Examples of a method for introducing a silicone side chain into the graft copolymer include a method using a radical polymerizable silicone macromonomer and a method using a polymer reaction. The method using a silicone macromonomer is useful in terms of the ease of the production process and economy.
[0015] シリコーンマクロモノマーは特に制限は受けないが、例えばリチウムトリアルキルシラ ノレートを開始剤とし、環状シロキサンをァニオン重合することによりリビングポリマー を得、それと γ—メタクリロキシプロピルジメチルモノクロロシランを反応させる方法（ 特開昭 59— 78236号公報）、または末端シラノール基含有シリコーンと γ メタタリ ロキシプロピルジメチルモノクロロシラン等の有機ケィ素化合物を縮合させる方法 (特 開昭 60— 123518号公報）等によって製造できる。  [0015] The silicone macromonomer is not particularly limited. For example, a living polymer is obtained by anionic polymerization of cyclic siloxane using lithium trialkylsilanolate as an initiator, and this is reacted with γ-methacryloxypropyldimethylmonochlorosilane. Or a method of condensing a terminal silanol group-containing silicone with an organic silicon compound such as γ-metataloxypropyldimethylmonochlorosilane (Japanese Patent Publication No. 60-123518). .
[0016] 上記シリコーンマクロモノマーとしては特に片末端に (メタ）アタリレートを導入したも のが好ましい。さらに、化学的安定性の観点から上記片末端に (メタ）アタリレートシリ コーンマクロモノマーの一方の末端は、アルキルシリル末端であることが好ましぐヒド ロキシ基、エポキシ基、アミノ基、アルコキシ基などの活性置換基が存在するのは望 ましくない。これらの市販品としては、例えば東亞合成 (株)製「ΑΚ— 5」、「ΑΚ— 30」 、「ΑΚ— 32」（いずれも商品名）や、信越化学 (株)製「Χ— 22— 174DX」、「X— 24 8201」、「X— 22— 2426」（いずれも商品名）等がある。  [0016] The silicone macromonomer is particularly preferably one in which (meth) acrylate is introduced at one end. Further, from the viewpoint of chemical stability, it is preferable that one end of the (meth) ate silyl silicone macromonomer at one end is an alkylsilyl end, a hydroxy group, an epoxy group, an amino group, an alkoxy group. It is not desirable for active substituents such as Examples of these commercial products include “ΑΚ-5”, “ΑΚ-30”, “ΑΚ-32” (all trade names) manufactured by Toagosei Co., Ltd., and “Χ-22-” manufactured by Shin-Etsu Chemical Co., Ltd. 174DX "," X-24 8201 "," X-22-22426 "(all trade names).
尚、上記シリコーンマクロモノマーは一種類のみでも或いは二種類以上を用いても よい。  The silicone macromonomer may be used alone or in combination of two or more.
[0017] 高分子反応によるシリコーン側鎖導入法としては、例えばエポキシシリコーン、シラ ノールシリコーン、ァミノシリコーン等の反応性シリコーンを用いる方法がある。具体的 には、主鎖中に導入したカルボン酸と片末端エポキシ変性シリコーンを反応させる方 法、主鎖中に導入したエポキシ基と片末端アミノ変性シリコーンを反応させる方法等 力 sある。 [0017] As a method for introducing a silicone side chain by a polymer reaction, for example, there is a method using reactive silicone such as epoxy silicone, silanol silicone, and aminoamino. Specifically, the main chain how the carboxylic acid is reacted with one end epoxy-modified silicone introduced into, a method such as force s reacting an epoxy group and one terminal amino-modified silicone introduced in the main chain.
[0018] シリコーン系側鎖の分子量としては、ポリスチレンを基準物質とするゲル浸透クロマ 卜グラフによる重量平均分子量で 3, 000-20, 000の範囲にあることカ好ましく、 3, 000-15, 000の範囲にあることがより好ましい。シリコーン系側鎖の重量平均分子 量が 3, 000未満の重合体では十分な耐擦過性が得られなくなり、また、重量平均分 子量が 20, 000を超えると、インクジェット吐出適性が劣る。  [0018] The molecular weight of the silicone side chain is preferably in the range of 3,000-20,000 in terms of weight average molecular weight according to gel permeation chromatograph using polystyrene as a reference substance, and 3,000-15,000. It is more preferable that it is in the range. When the weight average molecular weight of the silicone side chain is less than 3,000, sufficient scratch resistance cannot be obtained, and when the weight average molecular weight exceeds 20,000, the ink jet discharge suitability is poor.
[0019] [2]主鎖について グラフト共重合体を構成する主鎖は、エチレン性不飽和カルボン酸含有モノマーを 必須構成成分とし、所望によりその他の共重合可能なモノマーを構成成分とするが、 これらモノマーを共重合して得られるものである。 [0019] [2] Main chain The main chain constituting the graft copolymer has an ethylenically unsaturated carboxylic acid-containing monomer as an essential component, and optionally other copolymerizable monomers as components, and is obtained by copolymerizing these monomers. Is.
[0020] エチレン性不飽和カルボン酸含有モノマーとしては（メタ）アクリル酸、エタアクリル 酸、プロピルアクリル酸、イソプロピルアクリル酸、クロトン酸、ィタコン酸、フマル酸、シ トラコン酸、無水マレイン酸等がある力 S、その中でも（メタ）アクリル酸が好ましい。  [0020] Examples of the ethylenically unsaturated carboxylic acid-containing monomer include (meth) acrylic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, and maleic anhydride. Force S, among which (meth) acrylic acid is preferred.
[0021] エチレン性不飽和カルボン酸含有モノマーの導入量はグラフト共重合体の酸価が 40〜200mg KOH/g (固形分）になるように設定する必要力ぁり、 60〜； 150mg KOH/gになるように設定するのがより好ましい。酸価が 40mg KOH/g未満 の共重合では十分な水溶性が得られず、また、酸価が 200mg— KOH/gを超える とコーティング膜の耐水性が不十分となる。  [0021] The amount of the ethylenically unsaturated carboxylic acid-containing monomer to be introduced should be set so that the acid value of the graft copolymer is 40 to 200 mg KOH / g (solid content), 60 to 150 mg KOH / It is more preferable to set so as to be g. Copolymerization with an acid value of less than 40 mg KOH / g does not provide sufficient water solubility, and when the acid value exceeds 200 mg-KOH / g, the water resistance of the coating film becomes insufficient.
[0022] 後述するその他のモノマーを、本発明のグラフト共重合体の機能を損なわない範囲 で、主鎖を構成する所望成分として含有させることができる。  [0022] Other monomers to be described later can be contained as desired components constituting the main chain as long as the function of the graft copolymer of the present invention is not impaired.
その他のモノマーとしては、ビュル芳香族モノマー、スルホン酸含有モノマー、 （メタ )アクリル酸アルキル類、脂環式 (メタ）アタリレート、 （メタ）アクリル酸ヒドロキシアルキ ル類、 （メタ）アクリルアミド、酢酸ビュル、 N—ビュルピロリドン、 （メタ）アクリロニトリル 及び (メタ）アクリル酸等が挙げられる。また、 1分子中に 2個以上のビュル基を有する リレート、エチレングリコールジ（メタ）アタリレート、ポリエチレングリコールジ（メタ）ァク リレート、ポリプロピレングリコールジ（メタ）アタリレート、トリメチロールプロパントリ（メタ )アタリレート、ジ (メタ）アタリロキシェチルホスフェイト、トリァリルシアヌレート、トリァリ ノレイソシァヌレート、ジビュルベンゼン、マレイン酸ジァリルエステル、ポリアリルサッカ ロース等の架橋性モノマー等を含んでもよい。  Other monomers include butyl aromatic monomers, sulfonic acid-containing monomers, alkyl (meth) acrylates, alicyclic (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylamide, and acetic acid butyl. N-Buylpyrrolidone, (meth) acrylonitrile, (meth) acrylic acid and the like. In addition, relates, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol propane tri (meth) having two or more butyl groups in one molecule. ) Crosslinkable monomers such as attalylate, di (meth) attaryloxetyl phosphate, triarylcyanurate, triarynoisocyanurate, dibutylbenzene, maleic acid diaryl ester, polyallyl saccharose and the like may also be included.
[0023] 前記ビュル芳香族モノマーとしては、スチレン系モノマーであるスチレン、 α—メチ ノレスチレン、 ο メチルスチレン、 m メチルスチレン、 p メチルスチレン、 p— tert— ブチルスチレン、ビュルトルエンの他、フエニル基含有（メタ）アタリレート類としてベン ジル（メタ）アタリレート、フエニル（メタ）アタリレート、 2 ヒドロキシ一 3 フエノキシプ 口ピル（メタ）アタリレート、フエノキシェチル（メタ）アタリレート、フエノキシポリエチレン グリコール (メタ）アタリレート等が挙げられる。 [0023] The butyl aromatic monomers include styrene monomers such as styrene, α-methylol styrene, ο-methyl styrene, m-methyl styrene, p-methyl styrene, p-tert-butyl styrene, butyltoluene, and phenyl groups. Benzyl (meth) acrylate, (meth) acrylate, (hydroxy) 3 phenoxy pills (meth) acrylate, phenoxychetyl (meth) acrylate, phenoxy polyethylene Examples include glycol (meth) acrylate.
[0024] 前記スルホン酸含有モノマーとしては（メタ）アクリル酸 2—スルホン酸ェチル、スチ レンスルホン酸、 2—アクリルアミドー 2—メチルプロパンスルホン酸、ビニルスルホン 酸、（メタ）ァリルスルホン酸等が挙げられる。  [0024] Examples of the sulfonic acid-containing monomer include (meth) acrylic acid 2-ethyl sulfonate, styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, (meth) aryl sulfonic acid, and the like. .
[0025] 前記 (メタ）アクリル酸アルキル類の具体例としては、（メタ）アクリル酸メチル、（メタ） アクリル酸ェチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アタリノレ 酸 2—ェチルへキシル等が挙げられる。  [0025] Specific examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) atalinoleic acid. Examples include 2-ethylhexyl.
[0026] 前記脂環式 (メタ）アタリレートとしては、シクロペンチル (メタ）アタリレート、シクロへ キシル (メタ）アタリレート、シクロォクチル (メタ）アタリレート、シクロノニル (メタ）アタリ レート、イソボルニル（メタ）アタリレート、ノルボルニル（メタ）アタリレート、ジシクロペン タニル（メタ）アタリレート、ジシクロペンテュル（メタ）アタリレート、ジシクロペンテュル ォキシアルキル (メタ）アタリレート、ァダマンチル (メタ）アタリレートなどが挙げられる。  [0026] Examples of the alicyclic (meth) acrylate include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate, isobornyl (meth) acrylate. And rate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyalkyl (meth) acrylate and adamantyl (meth) acrylate.
[0027] 前記（メタ）アクリル酸ヒドロキシアルキル類の具体例としては、 2—ェチルへキシル（ メタ）アタリレート、 3—ヒドロキシプロピル（メタ）アタリレート、ポリアルキレングリコール（ n = 2〜30) (メタ）アタリレート、ポリ力プロラタトン (メタ）アタリレート等が挙げられる。 ただし、これらアクリル酸ヒドロキシアルキル類の導入量はグラフト共重合体の水酸基 価が 30mg— KOH/g以下になるよう設定されるのが好ましぐ 10mg— KOH/g以 下になるよう設定されるのがより好ましい。グラフト共重合体の水酸基価が 30mg— K OHを上回る場合は、グラフト共重合体を含む液の粘性が高くなるため、インクジエツ ト吐出適性が劣る。  [0027] Specific examples of the hydroxyalkyl (meth) acrylates include 2-ethylhexyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyalkylene glycol (n = 2 to 30) ( (Meth) acrylate, poly force prolatatatone (Meth) acrylate. However, the introduction amount of these hydroxyalkyl acrylates is preferably set so that the hydroxyl value of the graft copolymer is 30 mg-KOH / g or less, and preferably 10 mg-KOH / g or less. Is more preferable. When the hydroxyl value of the graft copolymer is more than 30 mg—K OH, the viscosity of the liquid containing the graft copolymer becomes high, and the ink jet discharge suitability is poor.
[0028] 上記モノマーによって構成される主鎖において、下記式（1)から求められる設計ガ ラス転移温度（Tg)が 10〜； 100°Cの範囲にあるのが好ましく、 20〜80°Cの範囲にあ るのがより好ましく、 50〜80°Cの範囲にあるのが特に好ましい。主鎖のガラス転移温 度が 10°Cより低い場合にはグラフト共重合体を含むコーティング剤が膜を形成した 際に十分な耐擦過性が得られず、 100°Cより高い場合には室温での膜の形成が困 難になる。  [0028] In the main chain composed of the monomer, the design glass transition temperature (Tg) obtained from the following formula (1) is preferably in the range of 10 to 100 ° C, and preferably 20 to 80 ° C. More preferably, it is in the range, and particularly preferably in the range of 50 to 80 ° C. When the glass transition temperature of the main chain is lower than 10 ° C, the coating agent containing the graft copolymer cannot provide sufficient scratch resistance when forming a film, and when it is higher than 100 ° C, the room temperature is room temperature. It becomes difficult to form a film at this point.
[0029] [数 1] 1/Tg= (Wl/Tg l+w2/Tg2+ - · - +wn/Tgn) (1) 式中、 1, 2 · · nは、 構成するモノマー種類 [0029] [Equation 1] 1 / Tg = ( Wl / T gl + w 2 / Tg 2 + --- + w n / Tg n ) (1) where 1, 2
Tgn ： nモノマーの単一重合体のガラス転移温度 （K) Tg n : Glass transition temperature of single polymer of n monomer (K)
wn：構成中の nモノマー単位の重量比 w n : weight ratio of n monomer units in the composition
Tg ： ガラス転移温度 （K)  Tg: Glass transition temperature (K)
[0030] [3]グラフト共重合体について [0030] [3] Graft copolymer
本発明のコーティング剤は、前記構成の [1]シリコーン系側鎖と [2]主鎖からなるグ ラフト共重合体を必須成分とするが、側鎖を含まない直鎖状共重合体を含有してもよ い。  The coating agent of the present invention contains a linear copolymer containing [1] silicone side chain and [2] main chain having the above-described constitution as an essential component but not containing a side chain. You can do it.
[0031] 上記側鎖を含まない直鎖状共重合体は、インクジェット適性の悪化やコーティング 膜の性能低下を防ぐ観点から、上記グラフト共重合体で記載した [2]主鎖を構成する モノマーと同じ構成のモノマーからなる共重合体で、酸価やガラス転移温度 (Tg)な どは上記 [2]主鎖の項に従う。  [0031] From the viewpoint of preventing deterioration of ink jet suitability and deterioration of the performance of the coating film, the linear copolymer not containing the side chain is [2] a monomer constituting the main chain described in the above graft copolymer. It is a copolymer composed of monomers of the same structure, and the acid value, glass transition temperature (Tg), etc., follow the above [2] main chain term.
[0032] グラフト共重合体の合成方法としてはマクロモノマー法、イオン重合法、高分子反 応による側鎖の導入などが知られている力 本発明のグラフト共重合体を合成するに は、側鎖の末端へのイオン性官能基の導入の容易さ、主鎖と側鎖の重合度の調整 及び主鎖と側鎖の連結を容易に行えるマクロモノマー法が最適である。  [0032] Known methods for synthesizing the graft copolymer include macromonomer method, ionic polymerization method, introduction of side chain by polymer reaction, etc. In order to synthesize the graft copolymer of the present invention, The macromonomer method is most suitable because it is easy to introduce an ionic functional group at the end of the chain, adjust the degree of polymerization of the main chain and side chain, and easily connect the main chain to the side chain.
[0033] 例えば、具体的に例示すると、本発明のグラフト共重合体は、側鎖を構成するシリコ ーンマクロモノマーを、主鎖を構成するエチレン性不飽和カルボン酸含有モノマーと 共に、或いはこれらに更に所望によりその他のモノマーを加えたものと共に共重合し て得ること力 Sでさる。  [0033] For example, as a specific example, the graft copolymer of the present invention includes a silicone macromonomer constituting a side chain together with an ethylenically unsaturated carboxylic acid-containing monomer constituting a main chain, or these In addition, it can be obtained by copolymerizing with other monomers added if desired.
[0034] また、共重合体中のカルボン酸は、その一部もしくは全てが塩基により中和されるこ とによりイオン化されている必要がある。中和に用いる塩基としては水酸化カリウム、 水酸化ナトリウム等のアルカリ金属水酸化物等の無機アルカリ剤、ジエタノールァミン 、トリエタノールァミン等の有機アミン類等が挙げられる力 インクジェット適性の観点 力もアルカリ金属水酸化物が好まし!/、。  [0034] The carboxylic acid in the copolymer must be ionized by neutralizing a part or all of it with a base. Examples of bases used for neutralization include inorganic alkali agents such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and organic amines such as diethanolamine and triethanolamine. Alkali metal hydroxide is preferred!
[0035] グラフト共重合体の合成において、シリコーンマクロモノマーなどグラフト側鎖を構 成するセグメントの重量割合が 10〜80重量％、それに対応して主鎖を構成するモノ マーの合計重量が 90〜20重量％であることが好ましぐさらに好ましくは構成するグ ラフト側鎖の重量割合が 15〜50重量％、それに対応して主鎖を構成するモノマーの 合計重量 85〜50重量％であり、もっとも好ましくは構成するグラフト側鎖の重量割合 カ 0〜40重量％、それに対応して主鎖を構成するモノマーの合計重量 80〜60重 量％である。グラフト側鎖の重量割合が 10重量％を下回った場合にはシリコーン成 分の不足から滑性付与効果が出ないため十分な耐擦過性が得られなくなり、 80重量 %を超える場合には主鎖を構成する成分の不足からコーティング膜を形成する能力 が劣るため耐擦過性が低下する。 [0035] In the synthesis of the graft copolymer, the weight ratio of the segment constituting the graft side chain such as a silicone macromonomer is 10 to 80% by weight, and the corresponding monomer constituting the main chain. It is preferred that the total weight of the mer is 90 to 20% by weight, more preferably 15% to 50% by weight of the constituting graph side chain, and the corresponding total weight of monomers constituting the main chain 85 It is ˜50% by weight, and most preferably, the weight ratio of the constituting graft side chain is 0 to 40% by weight, and the total weight of the monomers constituting the main chain correspondingly is 80 to 60% by weight. If the weight ratio of the graft side chain is less than 10% by weight, the effect of imparting lubricity will not be obtained due to the lack of silicone components, and sufficient scratch resistance will not be obtained. Since the ability to form a coating film is inferior due to the lack of the components that make up, the scratch resistance decreases.
[0036] グラフト共重合体の合成は、重合操作および分子量の調整が容易なことから、ラジ カル重合開始剤を用いる方法が好ましぐまた疎水性モノマーが水に溶解しにくいこ とから、有機溶剤中で重合させる溶液重合法が好ましレ、。 [0036] The synthesis of the graft copolymer is easy because the polymerization operation and the adjustment of the molecular weight are easy, so the method using a radical polymerization initiator is preferred, and the hydrophobic monomer is difficult to dissolve in water. A solution polymerization method in which polymerization is performed in a solvent is preferred.
溶液重合法でラジカル重合を行う際に好ましい溶剤としては、アセトン、メチルェチ ノレケトン、メチルイソブチルケトン等のケトン系溶剤、酢酸ェチル、酢酸ブチル等の酢 酸エステル系溶剤、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶剤、ブタ ノーノレ、イソプロパノーノレ、エタノーノレ、メタノーノレ、シクロへキサン、テトラヒドロフラン 、ジメチルホルムアミド、ジメチルスルホキシドおよびへキサメチルホスホアミド等が挙 げられ、より好ましくは、ケトン系溶剤、酢酸エステル系溶剤およびアルコール系溶剤 である。  Preferred solvents for radical polymerization by the solution polymerization method include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetate solvents such as ethyl acetate and butyl acetate, and aromatic solvents such as benzene, toluene and xylene. Group hydrocarbon solvents, butanol, isopropanol, ethanol, methanol, cyclohexane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoamide, and more preferably ketone solvents, acetic acid. These are ester solvents and alcohol solvents.
[0037] ラジカル重合開始剤としては、一般に用いられているものなら使用可能で、具体的 には、パーォキシケタール、ハイド口パーオキサイド、ジアルキルパーオキサイド、ジ ァシルバーオキサイド、パーォキシジカーボネート、パーォキシエステル、シァノ系の ァゾビスイソブチロニトリル、ァゾビス（2—メチルブチロニトリル）、非シァノ系のジメチ ルー 2, 2'ーァゾビスイソブチレート等が挙げられる。分子量の制御がしゃすぐ分解 温度の低い有機過酸化物やァゾ系化合物が好ましぐ特にァゾ系化合物がより好ま しい。  [0037] As the radical polymerization initiator, those generally used can be used, and specifically, peroxyketal, hydrated peroxide, dialkyl peroxide, disilver oxide, peroxydicarbonate. , Peroxyesters, cyano-based azobisisobutyronitrile, azobis (2-methylbutyronitrile), non-cyano-based dimethyl 2,2'-azobisisobutyrate, and the like. The molecular weight is controlled quickly. Decomposition of organic peroxides and azo compounds with low temperatures is preferred, especially azo compounds.
重合開始剤の使用量は、重合性モノマーの総重量に対して、 0. ；!〜 15重量％が 好ましぐさらに好ましくは 0. 3〜； 10重量％である。  The polymerization initiator is used in an amount of preferably 0.3 to 15% by weight, more preferably 0.3 to 10% by weight, based on the total weight of the polymerizable monomers.
[0038] また、グラフト共重合体の分子量を調整するために、メルカプト酢酸、メルカプトプロ ピオン酸、 2—プロパンチオール、 2—メルカプトエタノール、チォフエノール、ドデシ ノレメルカプタン、チォグリセロール等の連鎖移動剤を重合系に適量添加してもよい。 [0038] In order to adjust the molecular weight of the graft copolymer, mercaptoacetic acid, mercaptopro An appropriate amount of a chain transfer agent such as pionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecinoremercaptan, thioglycerol may be added to the polymerization system.
[0039] 好ましい重合温度は 40〜； 180°C、さらに好ましくは 50〜； 150°Cである。好ましい重 合時間は 3〜25時間である。  [0039] The polymerization temperature is preferably 40 to 180 ° C, more preferably 50 to 150 ° C. The preferred polymerization time is 3 to 25 hours.
[0040] 本発明のグラフト共重合体の分子量は、ポリスチレンを基準物質とするゲル浸透ク 口マトグラフによる重量平均分子量で 5, 000—30, 000の範囲であり、 8, 000—25 , 000の範囲カより好ましく、 10, 000〜20, 000の範囲カ特に好ましレヽ。重量平均 分子量が 5, 000未満の重合体では十分な耐擦過性が得られなくなり、また、重量平 均分子量が 30, 000を超えると、インクジェット吐出適性が劣る。  [0040] The molecular weight of the graft copolymer of the present invention is in the range of 5,000 to 30,000 as a weight average molecular weight by gel permeation chromatography using polystyrene as a reference substance, and is 8,000 to 25,000. The range is more preferable, and the range of 10,000 to 20,000 is particularly preferable. If the polymer has a weight average molecular weight of less than 5,000, sufficient scratch resistance cannot be obtained, and if the weight average molecular weight exceeds 30,000, the ink jet discharge suitability is poor.
[0041] 1.2 水性コーティング剤の使用方法  [0041] 1.2 Use of water-based coating agent
本発明の水性コーティング剤は、通常使用されている従来公知の顔料インクと共に 使用できる。本発明の水性コーティング剤と共に用いる顔料インクは、水性顔料イン ク、溶剤性顔料インク!/ヽずれにも適用可能であり特に制限を受けな!/、が、水性顔料ィ ンクと共に用いる方が好ましレ、。  The aqueous coating agent of the present invention can be used with conventionally known pigment inks that are usually used. The pigment ink used with the water-based coating agent of the present invention is applicable to water-based pigment inks and solvent-based pigment inks, and is not particularly limited, but is preferably used with water-based pigment inks. Masle.
例えば、水性コーティング剤を、水性顔料インクに添加して使用することができ、また 、顔料インクとは別に、水性コーティング液としてインクタンクに充填し、顔料インクと は別のノズルから吐出して使用することもできる。とくに、表面に緻密な膜を形成でき る点で後者がより望ましい。  For example, a water-based coating agent can be used by adding to a water-based pigment ink. In addition to the pigment ink, the ink tank is filled as a water-based coating liquid, and discharged from a nozzle separate from the pigment ink. You can also In particular, the latter is more preferable because a dense film can be formed on the surface.
[0042] 以下に、顔料インクと配合して!/、な!/、水性コーティング液及び、水性コーティング剤 を配合させた水性顔料インクについて説明する。 [0042] Hereinafter, the aqueous pigment ink blended with the pigment ink! /, Na! /, The aqueous coating liquid, and the aqueous coating agent will be described.
[0043] 2.水十生コーティング ί夜 [0043] 2. Water Jumei Coating ί 夜
本発明の水性コーティング液は、前記 1.水性コーティング剤のほか、水性媒体が 必須成分として含有される。  The aqueous coating solution of the present invention contains an aqueous medium as an essential component in addition to the above-mentioned 1. aqueous coating agent.
[0044] 2.1 水性媒体 [0044] 2.1 Aqueous medium
水性媒体としては、水性コーティング液の乾燥防止と吐出安定性の確保の観点か ら、水及び水溶性有機溶剤の混合溶媒が好適である。水は、イオン交換水（脱イオン 水）であることが好ましい。  As the aqueous medium, a mixed solvent of water and a water-soluble organic solvent is preferable from the viewpoint of preventing drying of the aqueous coating liquid and ensuring ejection stability. The water is preferably ion exchange water (deionized water).
水溶性有機溶剤としては、メチルアルコール、エチルアルコール、 η—プロピルアル コール、イソプロピルアルコール、 n ブチルアルコール、 sec ブチルアルコーノレ、 t ert ブチルアルコール等の炭素数 1〜4のアルキルアルコール類、ジメチルホルム アミド、ジメチルァセトアミド等のアミド類、アセトン、ジアセトンアルコール等のケトン又 はケトアルコール類、テトラヒドロフラン、ジォキサン等のエーテル類、ポリエチレングリ コール、ポリプロピレングリコール等のポリアルキレングリコール類、エチレングリコー ノレ、プロピレングリコーノレ、ブチレングリコーノレ、 トリエチレングリコーノレ、 1 , 2—へキサ ンジォ一ノレ、 1 , 2, 6 へキサントリオ一ノレ、チォジグリコーノレ、へキシレングリコーノレ 、ジエチレングリコール等のアルキレン基が 2〜6個の炭素原子を含むアルキレンダリ コーノレ類、グリセリン、エチレングリコールモノメチル（又はェチル）エーテル、ジェチ レングリコールメチル（又はェチル）エーテル、トリエチレングリコールモノメチル（又は ェチル）エーテル等の多価アルコールの低級アルキルエーテル類、 N メチノレー 2 ピロリドン、 2 ピロリドン、 1 , 3 ジメチルー 2 イミダゾリジノン等が挙げられる。こ れらの水溶性有機溶剤の中でも、ジエチレングリコール等の多価アルコール、トリエ チレングリコールモノメチル（又はブチル）エーテル等の多価アルコールの低級アル キルエーテルが好ましい。 Water-soluble organic solvents include methyl alcohol, ethyl alcohol, η-propyl alcohol Cholesterol, isopropyl alcohol, n butyl alcohol, sec butyl alcohole, t ert Alkyl alcohols having 1 to 4 carbon atoms such as butyl alcohol, amides such as dimethylformamide, dimethylacetamide, acetone, diacetone alcohol, etc. Ketones or keto alcohols, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2- Alkylene glycols containing 2 to 6 carbon atoms, such as xanthdiol, 1, 2, 6 hexanetriol, thioglycol, hexylene glycol, diethylene glycol, and the like. Lower alkyl ethers of polyhydric alcohols such as phosphorus, ethylene glycol monomethyl (or ethyl) ether, jetylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, N-methylolene 2 pyrrolidone, 2 pyrrolidone, 1 , 3 dimethyl-2 imidazolidinone and the like. Among these water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or butyl) ether are preferable.
尚、上記の水溶性有機溶剤は、必要に応じ、単独で、或いは二種以上を組み合わ せて用いることができる。  In addition, said water-soluble organic solvent can be used individually or in combination of 2 or more types as needed.
2.2 その他の成分 2.2 Other ingredients
本発明の水性コーティング液には、前記水性コーティング剤及び水性媒体以外の その他の成分として、通常水性顔料インクに添加され得る公知慣用の各種添加剤を 添カロすること力 Sでさる。  In the aqueous coating liquid of the present invention, as a component other than the aqueous coating agent and the aqueous medium, various known and commonly used additives that can be usually added to the aqueous pigment ink are added with a force S.
このような添加剤には、界面活性剤、消泡剤、防腐剤、沈降防止剤、キレート剤、増 粘剤、防食剤、酸化防止剤等が挙げられる。界面活性剤としては、脂肪酸塩類、高 級アルコール硫酸エステル塩類、液体脂肪油硫酸エステル塩類、アルキルァリルス ルホン酸塩類等の陰イオン界面活性剤、ポリオキシエチレンアルキルエーテル類、ポ リオキシエチレンアルキルエステル類、ポリオキシエチレンソルビタンアルキルエステ ル類、アセチレンアルコール、アセチレングリコール等の非イオン性界面活性剤、ァ ルキルアミン塩、第 4級アンモニゥム塩等の陽イオン性界面活性剤、アルキルべタイ ン、アルキルアミンオキサイド等の両性界面活性剤が挙げられる。 Such additives include surfactants, antifoaming agents, preservatives, anti-settling agents, chelating agents, thickeners, anticorrosives, antioxidants and the like. Surfactants include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkylaryl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, Nonionic surfactants such as polyoxyethylene sorbitan alkyl esters, acetylene alcohol and acetylene glycol, cationic surfactants such as alkylamine salts and quaternary ammonium salts, alkylbeta And amphoteric surfactants such as alkylamine oxide.
[0046] 2.3 水性コーティング液の調製方法 [0046] 2.3 Method for preparing aqueous coating solution
本発明の水性コーティング液に含まれる前記のグラフト共重合体の量は、水性コー ティング液全重量に対して、 0. ；!〜 30重量％の範囲が好ましぐ 2〜； 15重量％の範 囲がより好ましい。  The amount of the graft copolymer contained in the aqueous coating solution of the present invention is preferably in the range of 0.;! To 30% by weight, based on the total weight of the aqueous coating solution, 2 to 15% by weight. The range is more preferable.
[0047] 水性コーティング液に含まれる水溶性有機溶剤の量は、水性コーティング液全重 量に対して 3〜50重量％の範囲が好ましぐ 5〜40重量％の範囲がより好ましい。ま た、本発明の水性コーティング液に含まれる水の量は、 10〜90重量％の範囲が好 ましぐ 30〜90重量％の範囲がより好ましい。  [0047] The amount of the water-soluble organic solvent contained in the aqueous coating liquid is preferably in the range of 3 to 50% by weight, more preferably in the range of 5 to 40% by weight with respect to the total weight of the aqueous coating liquid. The amount of water contained in the aqueous coating solution of the present invention is preferably in the range of 10 to 90% by weight, more preferably in the range of 30 to 90% by weight.
[0048] また、水性コーティング液の pHは 5〜； 10の範囲が好ましい。 pHをこの範囲とするこ とで、前記グラフト共重合体を含む水性コーティング剤の溶解性を向上させ、保存安 定性を向上させること力 Sできる。しかも、水性コーティング液が適用される装置 (例え ばインクジェット記録装置）の部材の腐食を抑制することもできる。  [0048] The pH of the aqueous coating solution is preferably in the range of 5 to 10; By setting the pH within this range, it is possible to improve the solubility of the aqueous coating agent containing the graft copolymer and improve the storage stability. In addition, corrosion of members of an apparatus to which the aqueous coating liquid is applied (for example, an ink jet recording apparatus) can be suppressed.
[0049] 水性コーティング液の pH調整には、水酸化ナトリウム、水酸化カリウム等のアルカリ 金属水酸化物等の無機アルカリ剤、ジメチルエタノールァミン、ジエタノールァミン、ト リエタノールアミン等の有機アミン類、及びクェン酸、酒石酸等の有機酸、塩酸、リン 酸等の鉱酸等が pH調整剤として用いることができる。  [0049] To adjust the pH of the aqueous coating solution, inorganic alkali agents such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic amines such as dimethylethanolamine, diethanolamine and triethanolamine are used. Further, organic acids such as citrate and tartaric acid, mineral acids such as hydrochloric acid and phosphoric acid, and the like can be used as pH adjusters.
[0050] 水性コーティング液はインクジェット吐出信頼性の観点から 25°Cにおける粘度が 10 mPa ' s以下に抑えられていることが望ましぐ 5mPa' s以下に抑えられていることがよ り好ましい。  [0050] The water-based coating liquid preferably has a viscosity at 25 ° C of 10 mPa's or less, more preferably 5 mPa's or less, from the viewpoint of inkjet ejection reliability.
[0051] 3.水性コーティング剤を配合した水性顔料インク  [0051] 3. Water-based pigment ink containing water-based coating agent
3.1 顔料  3.1 Pigments
当該水性顔料インクに用いる顔料は、無機顔料及び有機顔料の!/、ずれであっても よい。これらは、必要に応じて、単独で、または組み合わせて用いることができる。  The pigment used in the water-based pigment ink may be an inorganic pigment or an organic pigment! /. These can be used alone or in combination as required.
[0052] 顔料の分散粒子径は、好ましくは、 0. 005〃 111〜15〃 111、さらに好ましくは 0. 05 〜5 111、最も好ましくは 0· 01〜1 111である。分散粒子径が 0· 005 m以下では 分散を安定化させるために分散剤をより多く必要とし顔料自身の性能が発揮できず、 また、 15 m以上では分散状態を安定に保つことが困難となる。 [0053] 無機顔料としては、カーボンブラック、酸化チタン等の金属酸化物、金属硫化物、 金属塩化物等が挙げられる。 [0052] The dispersed particle size of the pigment is preferably 0.005 to 111 to 111, more preferably 0.05 to 5111, and most preferably 0.01 to 1111. If the dispersed particle size is 0.005 m or less, more dispersant is required to stabilize the dispersion, and the pigment itself cannot perform, and if it is 15 m or more, it is difficult to keep the dispersion state stable. . [0053] Examples of inorganic pigments include metal oxides such as carbon black and titanium oxide, metal sulfides, and metal chlorides.
カーボンブラックとしては、ファーネスブラック、サーマルランプブラック、アセチレン ブラック、チャンネルブラック等が挙げられる。具体的には、 No.2300, No.900, MCF8 8, No.33, No.40, No.45, No.52, MA7, MA8, Νο·2200Β (以上三菱化学 (株)製、商品 名）、 RAVEN1255 (コロンビア社製、商品名）、 REGAL400R, REGAL330R, REGAL66 OR, MOGUL L (以上キャボット社製、商品名）、 Color Black FW1 , Color Black FW18 , Color Black S160, Color Black S170, Color Black S150, Color Black FW200, Col or Black FW2, Color Black FW2V, Printex35, Printex75, PrintexL6, Printex95, Pri ntex U (以上デグサ社製、商品名）等が挙げられる。  Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black. Specifically, No.2300, No.900, MCF8 8, No.33, No.40, No.45, No.52, MA7, MA8, Νο · 2200Β (Mitsubishi Chemical Corp. ), RAVEN1255 (Columbia, product name), REGAL400R, REGAL330R, REGAL66 OR, MOGUL L (Cabot, product name), Color Black FW1, Color Black FW18, Color Black S160, Color Black S170, Color Black S150 Color Black FW200, Col or Black FW2, Color Black FW2V, Printex35, Printex75, PrintexL6, Printex95, Pritex U (above, trade name, manufactured by Degussa).
[0054] 有機顔料としては、ァゾレーキ、不溶性ァゾ顔料、縮合ァゾ顔料、キレートァゾ顔料 等のァゾ顔料;フタロシアニン顔料、ペリレン顔料、ペリノン顔料、アントラキノン顔料、 キナクリドン顔料、ジォキサジン顔料、チォインジゴ顔料、イソインドリノン顔料、キノフ ラロン顔料等の多環式顔料;そのほかニトロ顔料、ニトロソ顔料、ァニリンブラックなど が挙げられる。  [0054] Organic pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, Polycyclic pigments such as indolinone pigments and quinophthalone pigments; nitro pigments, nitroso pigments, and aniline black are also included.
[0055] 有機顔料の具体例としては、本発明の水性コーティング剤を用い、得ようとする水 性顔料インクの種類（色）に応じて適宜挙げられる。例えば、 C丄 Pigment Yellow 1、 C .1. Pigment Yellow 2、 C.I. Pigment fellow «5、 C.I. Pigment ellow 13、 u.i. Pigment Yell ow 16、 C.I. Pigment Yellow 74、 C丄 Pigment Yellow 83、 C.I. Pigment Yellow 128等の 黄色威料； C.LPigment Red 5、 C.I. Pigment Red 7、 C.I. Pigment Red 12、 C.I. Pigment Red 48(Ca)、 C.LPigment Red 48(Mn)、 C.LPigment Red 57(Ca)、 C.LPigment Red 11 2、 C.LPigment Red 122等のマゼンタ色顔料； C丄 Pigment Blue 1、 C.LPigment Blue 2、 C.LPigment Blue 3、 C.LPigment Blue 15:3、 C.LPigment Blue 16、 C.LPigment Bl ue 22、 C.I.Vat Blue 4、 C.I. Vat Blue 6等のシアン色顔料等が挙げられる。  [0055] Specific examples of the organic pigment include the water-based coating agent of the present invention, and may be appropriately selected according to the type (color) of the water-based pigment ink to be obtained. For example, C 丄 Pigment Yellow 1, C .1. Pigment Yellow 2, CI Pigment fellow «5, CI Pigment ellow 13, ui Pigment Yell ow 16, CI Pigment Yellow 74, C 丄 Pigment Yellow 83, CI Pigment Yellow 128, etc. C.LPigment Red 5, CI Pigment Red 7, CI Pigment Red 12, CI Pigment Red 48 (Ca), C.LPigment Red 48 (Mn), C.LPigment Red 57 (Ca), C.LPigment Red 11 2, Magenta pigments such as C.LPigment Red 122; C 丄 Pigment Blue 1, C.LPigment Blue 2, C.LPigment Blue 3, C.LPigment Blue 15: 3, C.LPigment Blue 16, C.LPigment Bl and cyan pigments such as ue 22, CIVat Blue 4 and CI Vat Blue 6.
また、黒色インクの顔料としては、先記のカーボンブラック（C丄 Pigment Black 7)類 、酸化鉄顔料等の無機顔料のほかに、ァニリンブラック（C丄 Pigment Black 1)等の有 機顔料が挙げられる。  In addition to the above-mentioned inorganic pigments such as carbon black (C 丄 Pigment Black 7) and iron oxide pigments, organic pigments such as aniline black (C 丄 Pigment Black 1) are also included as black ink pigments. Can be mentioned.
[0056] 本発明の水性コーティング剤を水性顔料インクに添加して使用する場合には、コー ティング剤とは別に顔料を安定化させるため、顔料分散剤が水性顔料インク中に存 在することが望ましい。使用できる顔料分散剤については特に限定されないが、具体 的には、ァユオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、ノニォ ン性界面活性剤、水溶性高分子などが挙げられるが、顔料の分散安定性の観点か ら水溶性高分子分が特に好適である。 [0056] When the aqueous coating agent of the present invention is added to an aqueous pigment ink, In order to stabilize the pigment separately from the coating agent, it is desirable that a pigment dispersant is present in the aqueous pigment ink. The pigment dispersant that can be used is not particularly limited, and specific examples include a cationic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a water-soluble polymer. From the viewpoint of pigment dispersion stability, a water-soluble polymer is particularly preferred.
[0057] 水溶性高分子には、例えばポリアクリル酸、ポリメタクリル酸、（メタ）アクリル酸—（メ タ）アクリル酸エステル共重合体、スチレン （メタ）アクリル酸共重合体、スチレン一（ メタ）アクリル酸—（メタ）アクリル酸エステル共重合体、スチレン—マレイン酸共重合 体、およびこれらの塩等が挙げられる力 顔料に対して親和性を有する疎水性基を 有するモノマーと親水性基を有するモノマーとの共重合体が特に好ましい。  [0057] Examples of the water-soluble polymer include polyacrylic acid, polymethacrylic acid, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene (meth) acrylic acid copolymer, styrene ) Acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, and salts thereof, etc. A monomer having a hydrophobic group having affinity for a pigment and a hydrophilic group Particularly preferred are copolymers with the monomers they contain.
これらの水溶性高分子は、インクの粘度の観点から重量平均分子量が 3, 000〜2 0, 000の範囲にあるのが好ましい。また、インク中の含有量としては、 0. ；!〜 15重量 %の範囲が好ましい。  These water-soluble polymers preferably have a weight average molecular weight in the range of 3,000 to 20,000 from the viewpoint of ink viscosity. The content in the ink is preferably in the range of 0.;! To 15% by weight.
[0058] 3.2 その他  [0058] 3.2 Other
水性顔料インクには、前項 1.記載の水性コーティング剤のほか、上記の顔料、顔 料分散剤、及び前記 2.1水性媒体、 2.2その他の成分力 通常水性顔料インクで使用 される公知慣用の各種添加剤が添加される。これらの組成は、前項 2.と同様である In addition to the water-based coating agent described in the preceding paragraph 1, the water-based pigment ink includes the above-mentioned pigment, the pigment dispersant, and the above-mentioned 2.1 aqueous medium, 2.2 and other component powers. Agent is added. These compositions are the same as in the previous section 2.
〇 Yes
[0059] 3.3 水性顔料インクの調製方法  [0059] 3.3 Method for Preparing Aqueous Pigment Ink
水性コーティング剤を配合した水性顔料インクの場合、インクに含まれる顔料分散 剤の量は、インク全重量に対して、 0. ；!〜 30重量％の範囲が好ましぐ；!〜 15重量 %の範囲がより好ましい。また、水性インクに含まれる顔料の量は、 0. ；!〜 30重量％ の範囲が好ましぐ；!〜 15重量％の範囲がより好ましい。  In the case of an aqueous pigment ink containing an aqueous coating agent, the amount of the pigment dispersant contained in the ink is preferably in the range of 0.;! To 30% by weight with respect to the total weight of the ink;! To 15% by weight The range of is more preferable. The amount of the pigment contained in the water-based ink is preferably in the range of 0.;! To 30% by weight; more preferably in the range of! To 15% by weight.
水性顔料インクに含まれる顔料分散剤と顔料の含有比率は、 1： 1〜； 1： 30 (重量比 )の範囲であること力 S好ましく、 1： 2〜； 1： 15であることがより好まし!/、。  The content ratio of the pigment dispersant and the pigment contained in the water-based pigment ink is in the range of 1: 1 to 1:30 (weight ratio), preferably S, more preferably 1: 2 to 1:15. I like it!
[0060] 水性顔料インクに含まれる水溶性有機溶剤の量は、インク全重量に対して 3〜50 重量％の範囲が好ましぐ 3〜40重量％の範囲がより好ましい。また、水性顔料イン クに含まれる水の量は、 10〜90重量％の範囲が好ましぐ 30〜80重量％の範囲が より好ましい。 [0060] The amount of the water-soluble organic solvent contained in the aqueous pigment ink is preferably 3 to 50% by weight, more preferably 3 to 40% by weight based on the total weight of the ink. The amount of water contained in the aqueous pigment ink is preferably in the range of 10 to 90% by weight, and in the range of 30 to 80% by weight. More preferred.
[0061] また、水性顔料インクの pHは 5〜； 10の範囲が好ましい。 pHをこの範囲とすることで 、前記のコーティング剤や顔料分散剤の溶解性を向上させ、保存安定性を向上させ ること力 Sできる。しかも、水性顔料インクが適用される装置 (例えばインクジェット記録 装置）の部材の腐食を抑制することもできる。  [0061] The pH of the aqueous pigment ink is preferably in the range of 5 to 10; By setting the pH within this range, it is possible to improve the solubility of the coating agent and the pigment dispersant and improve the storage stability. Moreover, corrosion of members of an apparatus to which the aqueous pigment ink is applied (for example, an ink jet recording apparatus) can be suppressed.
[0062] 水性顔料インクの pH調整には、水酸化ナトリウム、水酸化カリウム等のアルカリ金 属水酸化物等の無機アルカリ剤、ジメチルエタノールァミン、ジエタノールァミン、トリ エタノールァミン等の有機アミン類、及びクェン酸、酒石酸等の有機酸、塩酸、リン酸 等の鉱酸等が pH調整剤として用いることができる。  [0062] To adjust the pH of the aqueous pigment ink, an inorganic alkali agent such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an organic amine such as dimethylethanolamine, diethanolamine or triethanolamine. And organic acids such as citrate and tartaric acid, mineral acids such as hydrochloric acid and phosphoric acid can be used as pH adjusters.
[0063] 水性コーティング剤を配合した水性顔料インクは、上記の水性顔料インクの各成分 と共に水性コーティング剤を混合して分散させることで、コーティング剤含有の水性顔 料インクが得られる。上記の各成分をそのまま、或いは必要に応じて乾燥防止剤や その他の添加剤を添加して、水性媒体で希釈してインクジェット記録用インク、水性 ボールペンやマーカーペンなどの筆記用具の水性顔料インクに使用することができ る。この場合、インクジェットノズルやペン先が乾燥により目詰まりするのを防ぐために 、上記の水溶性有機溶剤のうち、低揮発性又は不揮発性の溶剤を添加するとよい。 また、記録媒体への浸透性を高めるためには、揮発性の溶剤を添加するとよい。特 にインクジェット記録用水性顔料インクに使用する場合は、インクに適度な表面張力 を持たせるために、界面活性剤を添加することも好まし!/、。  [0063] A water-based pigment ink containing a water-based coating agent can be obtained by mixing and dispersing the water-based coating agent together with the components of the water-based pigment ink. Add each of the above components as they are, or add anti-drying agents and other additives as necessary, and dilute with an aqueous medium to prepare ink-jet recording inks and water-based pigment inks for writing utensils such as water-based ballpoint pens and marker pens. Can be used. In this case, in order to prevent the inkjet nozzle and the nib from becoming clogged due to drying, it is preferable to add a low-volatile or non-volatile solvent among the above water-soluble organic solvents. In order to increase the permeability to the recording medium, a volatile solvent may be added. Especially when used in water-based pigment inks for inkjet recording, it is also preferable to add a surfactant to give the ink an appropriate surface tension!
[0064] 4.水性コーティング剤または水性コーティング液の使用方法  [0064] 4. Method of using aqueous coating agent or aqueous coating solution
以下に、上記水性コーティング液または水性コーティング剤を配合した水性顔料ィ ンクでのインクジェット記録方法について説明する。  Hereinafter, an ink jet recording method using an aqueous pigment ink containing the above aqueous coating liquid or aqueous coating agent will be described.
水性コーティング液または水性コーティング剤を配合した水性顔料インクを吐出す るインクジェット記録方式については特に制限を受けず公知の方法を用いることがで きる。特に、水性コーティング剤の高温時の安定性、コゲーシヨンの起こり難さから一 般に使用樹脂の選択範囲が狭いと言われるサーマルジェット方式にも好適である。 記録媒体については、特に制限を受けないが、表面にインク受容層を設けたインク ジェット記録用紙に、本発明の水性コーティング液または水性コーティング剤を配合 した水性顔料インクを適用することが特に有用である。 The ink jet recording method for discharging the aqueous pigment ink containing the aqueous coating liquid or the aqueous coating agent is not particularly limited, and a known method can be used. In particular, it is also suitable for a thermal jet method, which is generally said to have a narrow selection range of resin used due to the stability of aqueous coating agents at high temperatures and the difficulty of kogation. The recording medium is not particularly limited, but the water-based coating liquid or water-based coating agent of the present invention is added to the ink jet recording paper having an ink receiving layer on the surface. It is particularly useful to apply the prepared aqueous pigment ink.
[0065] 以下、特に、本発明の水性コーティング液を、顔料インクとは別のタンクに充填し、 別ノズルから吐出する場合の記録方法について詳説する。 Hereinafter, a recording method in the case where the aqueous coating liquid of the present invention is filled in a tank different from the pigment ink and discharged from another nozzle will be described in detail.
インクジェット方式による塗布においては、顔料インクを吐出後に水性コーティング 液を吐出する必要がある力 1台のインクジェットプリンタに記録媒体を一回給紙する In application by inkjet method, it is necessary to discharge the aqueous coating liquid after discharging the pigment ink. Feed the recording medium once to one inkjet printer.
(1パス）だけで顔料インクを用いたインクジェット記録工程と水性コーティング液によ る表面被膜形成工程を完了させるのが望ましレ、。 It is desirable to complete the ink jet recording process using pigment ink and the surface film forming process using an aqueous coating solution in only one pass.
[0066] 本発明の水性コーティング液の塗布は、顔料インクの存在する部分のみに行うこと も、顔料インクの有無にかかわらず全面に対して行うこともでき、特に制限は受けない 実施例 Application of the aqueous coating liquid of the present invention can be performed only on a portion where the pigment ink is present or on the entire surface regardless of the presence or absence of the pigment ink, and is not particularly limited.
[0067] 次に実施例及び比較例を挙げて本発明をさらに具体的に説明する。尚、以下の各 例における「％」及び「部」は、それぞれ「重量％」及び「重量部」を意味する。また、 T gは、シリコーン側鎖を除く主鎖の共重合体、または直鎖状共重合体の値として、前 記式（1)より算出したものである。  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following examples, “%” and “part” mean “% by weight” and “part by weight”, respectively. Further, T g is calculated from the above formula (1) as a value of a main chain copolymer excluding silicone side chains or a linear copolymer.
[0068] (実施例 1)  [Example 1]
<共重合体の合成 >  <Synthesis of copolymer>
撹拌機、滴下ロート、還流冷却器、窒素ガス導入管及び温度計を備えたガラスフラ スコに、メチノレメタクリレートを 25g、フ"チノレメタクリレートを 35g、メタクリノレ酸を 15g、重 量平均分子量 5, 000の片末端メタクリロイル変性ポリジメチルシロキサン（シリコーン マクロモノマー A)を 25g、イソプロピルアルコールを 200g、ァゾビス 2 メチロブチ ルニトリル (ABN— E)を 3. 5gを投入して 80°Cで 7時間重合させ、共重合体のイソプ 口ピルアルコール溶液（固形分 30%)を得た。続いて、共重合体のイソプロピルアル コール溶液に、該共重合体が有するカルボキシル基に対して当量の水酸化カリウム 及びイオン交換水を加えて中和した。そして、減圧下に脱溶剤してイソプロピルアル コールを留去し、共重合体 El (Mw: 12, 000、酸価 lOOmg— KOH Tg65°C) の水溶液（固形分 25%)を得た。  A glass flask equipped with a stirrer, dropping funnel, reflux condenser, nitrogen gas inlet tube and thermometer, 25 g of methylol methacrylate, 35 g of phenolic methacrylate, 15 g of methacrylolic acid, weight average molecular weight 5,000 25 g of one-terminal methacryloyl-modified polydimethylsiloxane (silicone macromonomer A), 200 g of isopropyl alcohol, and 3.5 g of azobis 2 methylobutyronitrile (ABN—E) were added and polymerized at 80 ° C for 7 hours. Then, an isopropyl alcohol solution (solid content 30%) of the coal was obtained, and then an equivalent amount of potassium hydroxide and ion-exchanged water with respect to the carboxyl group of the copolymer was added to the isopropyl alcohol solution of the copolymer. The solvent was removed under reduced pressure to distill off the isopropyl alcohol, and the copolymer El (Mw: 12,000, acid value lOOmg—KOH Tg65 ° C) Solution (solid content 25%) was obtained.
[0069] <水性コーティング液の調製〉 上記共重合体 Elの水溶液（固形分 25%) 20部、グリセリン 5部、ジエチレングリコ 一ノレ 15部、 2 ピロリドン 2部及びイオン交換水 58部を混合し、ジェチルエタノール ァミンで pHが 8〜； 10になるように調整し、ポアサイズ 5. C^ mのメンブランフィルター を用いて濾過し、 目的とする水性コーティング液 E1を得た。 [0069] <Preparation of aqueous coating solution> 20 parts of an aqueous solution of the above copolymer El (solid content 25%), 5 parts of glycerin, 15 parts of diethyleneglycol monoole, 2 parts of 2 pyrrolidone and 58 parts of ion-exchanged water are mixed, and pH is 8 to 8 with jetylethanolamine; It was adjusted to 10 and filtered using a membrane filter with a pore size of 5. C ^ m to obtain the target aqueous coating solution E1.
[0070] (実施例 2) [0070] (Example 2)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 14g、プチ ノレメタクリレー卜 38g、メタクリノレ酸 23g、シリコーンマクロモノマー A25giこ変更し、そ の他は実施例 1と同様に操作して、共重合体 E2 (Mw: 13, 000、酸価 150mg— K OH/g、 Tg65°C)の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性 コーティング液 E2を得た。  The monomer used in the synthesis of the copolymer of Example 1 was changed to 14 g of methyl methacrylate, 38 g of butyl methacrylate, 23 g of methacrylolic acid, A25gi of silicone macromonomer, and the other operations were the same as in Example 1. Thus, an aqueous solution of copolymer E2 (Mw: 13,000, acid value 150 mg—K OH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution E2 was obtained in the same manner as in Example 1.
[0071] (実施例 3) [Example 3]
実施例 1の共重合体の合成に使用するモノマー組成はそのままで、ァゾビス 2— メチロブチルニトリル (ABN— E)を 2. Ogに変更し、その他は実施例 1と同様に操作 して、共重合体 E3 (Mw: 22, 000、酸価 100mg— KOH/g、 Tg65°C)の水溶液を 得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 E3を得た。  The monomer composition used in the synthesis of the copolymer of Example 1 is kept as it is, azobis 2-methylobutylnitrile (ABN-E) is changed to 2. Og, and other operations are performed in the same manner as in Example 1. An aqueous solution of copolymer E3 (Mw: 22,000, acid value 100 mg—KOH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution E3 was obtained in the same manner as in Example 1.
[0072] (実施例 4) [Example 4]
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 34g、プチ ノレメタタリレート 33g、メタクリノレ酸 8g、シリコーンマクロモノマー A25gに変更し、ァゾ ビスー2—メチロブチルニトリル (ABN— E)を 2· Ogに変更し、その他は実施例 1と同 様に操作して、共重合体 E4 (Mw: 22, 000、酸価 50mg— KOH/g、 Tg65°C)の 水溶液を得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 E4を 得た。  The monomer used in the synthesis of the copolymer of Example 1 was changed to 34 g of methyl methacrylate, 33 g of petitenomethacrylate, 8 g of methacrylolic acid, and 25 g of silicone macromonomer, and azobis-2-methylobutylnitrile ( ABN—E) was changed to 2 · Og, and the others were operated in the same manner as in Example 1 to obtain an aqueous solution of copolymer E4 (Mw: 22,000, acid value 50 mg—KOH / g, Tg65 ° C). Got. Thereafter, an aqueous coating solution E4 was obtained in the same manner as in Example 1.
[0073] (実施例 5) [0073] (Example 5)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 23g、プチ ノレメタタリレート 33g、メタクリノレ酸 15g、 2 ヒドロキシェチノレメタタリレート 4g、シリコー ンマクロモノマー A25gに変更し、その他は実施例 1と同様に操作して、共重合体 E5 (Mw: 13, 000、酸価 lOOmg— KOH/g、水酸基価 17mg— KOH/g、 Tg65°C) の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 E5 を得た。 The monomer used for the synthesis of the copolymer of Example 1 was changed to 23 g of methyl methacrylate, 33 g of butyl methacrylate, 15 g of methacrylate, 2 g of hydroxyethenore methacrylate, and 25 g of silicone macromonomer A. The other procedures were carried out in the same manner as in Example 1 to obtain an aqueous solution of a copolymer E5 (Mw: 13,000, acid value lOOmg—KOH / g, hydroxyl value 17 mg—KOH / g, Tg65 ° C.). Thereafter, the aqueous coating solution E5 was further operated in the same manner as in Example 1. Got.
[0074] (実施例 6) [Example 6]
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 25g、プチ ルメタタリレート 35g、メタクリル酸 15g、重量平均分子量 12, 000の片末端メタクリロ ィル変性ポリジメチルシロキサン（シリコーンマクロモノマー B) 25gに変更し、その他 は実施例 1と同様に操作して、共重合体 E6 (Mw: 15, 000、酸価 lOOmg— KOH/ g、 Tg65°C)の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性コーテ イング液 E6を得た。  The monomer used for the synthesis of the copolymer of Example 1 was a methyl methacrylate 25 g, a methyl methacrylate 35 g, a methacrylic acid 15 g, and a one-terminal methacryloyl-modified polydimethylsiloxane (silicone macromolecule) having a weight average molecular weight of 12,000. Monomer B) was changed to 25 g, and the others were operated in the same manner as in Example 1 to obtain an aqueous solution of copolymer E6 (Mw: 15,000, acid value lOOmg—KOH / g, Tg 65 ° C.). Thereafter, an aqueous coating solution E6 was obtained in the same manner as in Example 1.
[0075] (実施例 7) [0075] (Example 7)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 10g、プチ ノレメタクリレー卜 25g、メタクリノレ酸 15g、シリコーンマクロモノマー A50giこ変更し、そ の他は実施例 1と同様に操作して、共重合体 E8 (Mw: 13, 000、酸価 lOOmg— K OH/g、 Tg65°C)の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性 コーティング液 E7を得た。  The monomer used for the synthesis of the copolymer of Example 1 was changed to 10 g of methyl methacrylate, 25 g of butyl methacrylate, 15 g of methacrylolic acid, and 50 g of silicone macromonomer, and the other operations were the same as in Example 1. Thus, an aqueous solution of a copolymer E8 (Mw: 13,000, acid value lOOmg—K OH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution E7 was obtained in the same manner as in Example 1.
[0076] (実施例 8) [Example 8]
実施例 1の共重合体の合成に使用するモノマーを、ブチルメタタリレート 60g、メタク リル酸 15g、シリコーンマクロモノマー A25gに変更し、その他は実施例 1と同様に操 作して、共重合体 E8 (Mw: 12, 000、酸価 100mg— KOH/g、Tg38°C)の水溶液 を得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 E9を得た。  The monomer used in the synthesis of the copolymer of Example 1 was changed to 60 g of butyl methacrylate, 15 g of methacrylic acid, and 25 g of silicone macromonomer, and the other operations were performed in the same manner as in Example 1 to obtain a copolymer. An aqueous solution of E8 (Mw: 12,000, acid value 100 mg—KOH / g, Tg 38 ° C.) was obtained. Thereafter, an aqueous coating solution E9 was obtained in the same manner as in Example 1.
[0077] (実施例 9) [0077] (Example 9)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 52g、プチ ノレメタタリレート 8g、メタクリノレ酸 15g、シリコーンマクロモノマー A25gに変更し、その 他は実施例 1と同様に操作して、共重合体 E10 (Mw: 12, 000、酸価 lOOmg— KO H/g、 TglOO°C)の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性 コーティング液 E9を得た。  The monomers used in the synthesis of the copolymer of Example 1 were changed to 52 g of methyl methacrylate, 8 g of butyl methacrylate, 15 g of methacrylolic acid, and 25 g of silicone macromonomer, and the other operations were the same as in Example 1. Thus, an aqueous solution of a copolymer E10 (Mw: 12,000, acid value lOOmg—KO H / g, TglOO ° C.) was obtained. Thereafter, an aqueous coating solution E9 was obtained in the same manner as in Example 1.
[0078] (比較例 1) [0078] (Comparative Example 1)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 40g、プチ ノレメタタリレート 45g、メタクリル酸 15gに変更し、その他は実施例 1と同様に操作して 、共重合体 CI (Mw: 13, 000、酸価 lOOmg KOH/g、 Tg65°C)の水溶液を得 た。その後、さらに実施例 1と同様に操作して、水性コーティング液 C1を得た。 The monomers used in the synthesis of the copolymer of Example 1 were changed to 40 g of methyl methacrylate, 45 g of butyl methacrylate, and 15 g of methacrylic acid, and the other operations were performed in the same manner as in Example 1. Then, an aqueous solution of copolymer CI (Mw: 13,000, acid value lOOmg KOH / g, Tg 65 ° C.) was obtained. Thereafter, the same operation as in Example 1 was further performed to obtain an aqueous coating solution C1.
[0079] (比較例 2) [0079] (Comparative Example 2)
実施例 1の共重合体の合成に使用するモノマーを、ブチルメタタリレート 41g、メタク リル酸 34g、シリコーンマクロモノマー A25gに変更し、その他は実施例 1と同様に操 作して、共重合体 C2 (Mw: 14, 000、酸価 220mg KOH/g、Tg65°C)の水溶液 を得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 C2を得た。  The monomer used in the synthesis of the copolymer of Example 1 was changed to 41 g of butyl methacrylate, 34 g of methacrylic acid, and 25 g of silicone macromonomer, and the others were operated in the same manner as in Example 1 to obtain a copolymer. An aqueous solution of C2 (Mw: 14,000, acid value 220 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution C2 was obtained in the same manner as in Example 1.
[0080] (比較例 3) [0080] (Comparative Example 3)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 38g、プチ ノレメタタリレート 32g、メタクリノレ酸 5g、シリコーンマクロモノマー A25gに変更し、その 他は実施例 1と同様に操作して、共重合体 C3 (Mw: 13, 000、酸価 33mg KOH /g、 Tg65°C)の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性コ 一ティング ί夜 C3を得た。  The monomers used for the synthesis of the copolymer of Example 1 were changed to 38 g of methyl methacrylate, 32 g of butyl methacrylate, 5 g of methacrylolic acid, and 25 g of silicone macromonomer, and the other operations were the same as in Example 1. An aqueous solution of copolymer C3 (Mw: 13,000, acid value 33 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, the same operation as in Example 1 was further carried out to obtain an aqueous coating film C3.
[0081] (比較例 4) [0081] (Comparative Example 4)
実施例 1の共重合体の合成に使用するモノマー組成はそのままで、ァゾビス 2— メチロブチルニトリル (ΑΒΝ— Ε)を 1. 2gに変更し、その他は実施例 1と同様に操作 して、共重合体 C4 (Mw: 35, 000、酸価 100mg KOH/g、Tg65°C)の水溶液を 得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 C4を得た。  The monomer composition used in the synthesis of the copolymer of Example 1 was kept as it was, and azobis 2-methylobutylnitrile (ΑΒΝ-Ε) was changed to 1.2 g, and the other operations were performed in the same manner as in Example 1. An aqueous solution of copolymer C4 (Mw: 35,000, acid value 100 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, the same operation as in Example 1 was further performed to obtain an aqueous coating solution C4.
[0082] (比較例 5) [0082] (Comparative Example 5)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 14g、プチ ルメタタリレート 52g、メタクリル酸 34gに変更し、その他は実施例 1と同様に操作して 、共重合体 C5 (Mw: 13, 000、酸価 220mg KOH/g、Tg65°C)の水溶液を得 た。その後、さらに実施例 1と同様に操作して、水性コーティング液 C5を得た。  The monomer used for the synthesis of the copolymer of Example 1 was changed to 14 g of methyl methacrylate, 52 g of methyl methacrylate, and 34 g of methacrylic acid, and the other operations were carried out in the same manner as in Example 1 to obtain copolymer C5. An aqueous solution (Mw: 13,000, acid value 220 mg KOH / g, Tg 65 ° C.) was obtained. Thereafter, an aqueous coating solution C5 was obtained in the same manner as in Example 1.
[0083] (比較例 6) [0083] (Comparative Example 6)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 40g、プチ ルメタタリレート 45g、メタクリル酸 15gに変更し、ァゾビス一 2 メチロブチルニトリル（ ABN— E)を 1. Ogに変更し、その他は実施例 1と同様に操作して、共重合体 C6 (M w: 42, 000、酸価 lOOmg KOH/g、 Tg65°C)の水溶液を得た。その後、さらに 実施例 1と同様に操作して、水性コーティング液 C6を得た。 The monomer used in the synthesis of the copolymer of Example 1 was changed to 40 g of methyl methacrylate, 45 g of methyl methacrylate, and 15 g of methacrylic acid, and 1. Og of azobis-2-methylobutylnitrile (ABN-E). The others were operated in the same manner as in Example 1 to obtain an aqueous solution of a copolymer C6 (Mw: 42,000, acid value lOOmg KOH / g, Tg65 ° C). Then further In the same manner as in Example 1, an aqueous coating solution C6 was obtained.
[0084] (比較例 7) [0084] (Comparative Example 7)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 35g、プチ ルメタタリレート 40g、メタクリル酸 15g、 2—ヒドロキシェチルメタタリレート 10gに変更 し、その他は実施例 1と同様に操作して、共重合体 C7 (Mw: 14, 000、酸価 lOOmg — KOH/g、水酸基価 43mg— KOH/g、 Tg65°C)の水溶液を得た。その後、さら に実施例 1と同様に操作して、水性コーティング液 C7を得た。  The monomer used for the synthesis of the copolymer of Example 1 was changed to 35 g of methyl methacrylate, 40 g of methyl methacrylate, 15 g of methacrylic acid, and 10 g of 2-hydroxyethyl methacrylate. The same operation was performed to obtain an aqueous solution of copolymer C7 (Mw: 14,000, acid value lOOmg—KOH / g, hydroxyl value 43 mg—KOH / g, Tg 65 ° C.). Thereafter, the same operation as in Example 1 was further performed to obtain an aqueous coating solution C7.
[0085] (比較例 8) [0085] (Comparative Example 8)
実施例 1の共重合体の合成に使用するモノマーを、メチルメタタリレート 21g、プチ ノレメタクリレー卜 31g、メタクリノレ酸 15g、 2—ヒドロキシェチノレメタクリレー卜 8g、シリコー ンマクロモノマー A25gに変更し、その他は実施例 1と同様に操作して、共重合体 C8 (Mw: 12, 000、酸価 lOOmg— KOH/g、水酸基価 35mg— KOH/g、 Tg65°C) の水溶液を得た。その後、さらに実施例 1と同様に操作して、水性コーティング液 C8 を得た。  The monomer used in the synthesis of the copolymer of Example 1 was changed to 21 g of methyl methacrylate, 31 g of petitenomethacrylate 、, 15 g of methacrylolic acid, 8 g of 2-hydroxyethylenomethacrylate 卜, and 25 g of silicone macromonomer A, The other procedures were carried out in the same manner as in Example 1 to obtain an aqueous solution of a copolymer C8 (Mw: 12,000, acid value lOOmg—KOH / g, hydroxyl value 35 mg—KOH / g, Tg65 ° C.). Thereafter, an aqueous coating solution C8 was obtained in the same manner as in Example 1.
[0086] [評価] [0086] [Evaluation]
実施例 1〜 9及び比較例 1〜 8で得られた、水性コーティング液 E 1〜E9及び C 1〜 C8について、下記 a)〜c)の項目に関して評価を行った。その結果を表 1及び 2に示 す  The following items a) to c) were evaluated for the aqueous coating solutions E 1 to E9 and C 1 to C8 obtained in Examples 1 to 9 and Comparative Examples 1 to 8. The results are shown in Tables 1 and 2.
[0087] <記録物の作成〉  [0087] <Creation of recorded material>
各水性コーティング液及び顔料インクをマイクロバブルジェットプリンタ（登録商標） ( キャノン (株)製 PIXUS iP4200、商品名）のインクカートリッジに充填し、市販の光 沢紙 (キャノン (株)製 フォト光沢紙 GP— 301、商品名）に黒顔料インクでの印字を 行い、続!、てインクジェット方式による水性コーティング液の塗布を行った。  Each water-based coating liquid and pigment ink are filled into an ink cartridge of a micro bubble jet printer (registered trademark) (PIXUS iP4200, trade name, manufactured by Canon Inc.) — 301, trade name) was printed with black pigment ink, followed by application of an aqueous coating solution by the inkjet method.
尚、マイクロバブルジェットプリンタはキャノン株式会社の登録商標である。  Microbubble jet printer is a registered trademark of Canon Inc.
[0088] [a]耐擦過性 [0088] [a] Scratch resistance
上記操作によって作成した記録物を室温で 24時間乾燥させた後、印字部分を指 で強く擦った。その際の変化を以下の基準に基づき評価した。  The recorded matter prepared by the above operation was dried at room temperature for 24 hours, and then the printed portion was rubbed with fingers. Changes at that time were evaluated based on the following criteria.
〇：印字の剥がれがほとんど認められない。 Δ：印字の剥がれがある程度認められる。 ○: Peeling of the print is hardly recognized. Δ: Some peeling of printing is recognized.
X：印字の剥がれが明らかに認められる。  X: Print peeling is clearly recognized.
[0089] [b]耐水性 [0089] [b] Water resistance
記録物の上に水ある!/、は水：ダリセリン：ジエチレンダリコール： 2—ピロリドン = 78： 5 : 15 : 2からなる溶液 Aをスポットして 3分間放置し、インクの滲みを以下の基準に基 づき評価した。  There is water on the recorded material! /, Ha: Water: Daricelin: Diethylene Daricol: 2-Pyrrolidone = 78: 5: 15: 2 Spot A and let stand for 3 minutes. The evaluation was based on this.
◎：水でも溶液 Aでもインク滲みが確認されな!/、。  A: Ink bleeding is not confirmed in either water or solution A! /.
〇：インク滲みが水では確認されな!/、が溶液 Aで僅かに確認される。  ◯: Ink bleeding is not confirmed in water! / Is slightly confirmed in solution A.
△：水でも溶液 Aでもある程度のインク滲みが確認される。  Δ: Some degree of ink bleeding is confirmed in both water and solution A.
X：水でも溶液 Aでも明らかなインク滲みが確認される。  X: Obvious ink bleeding is observed in both water and solution A.
[0090] [c]光沢 [0090] [c] Gloss
水性コーティング液を用いてレ、なレ、顔料インク印字画像をコントロールとして各記録 物の光沢を以下の基準に基づき目視で評価した。  The gloss of each recorded matter was visually evaluated based on the following criteria using an aqueous coating solution as a control.
〇：コントロールと比較して明確な光沢向上が認められる。  ◯: A clear improvement in gloss is recognized as compared with the control.
△：コントロールと比較してある程度の光沢向上が認められる。  (Triangle | delta): The gloss improvement to some extent is recognized compared with control.
X：コントロールと比較して光沢向上が認められない、もしくは低下している。  X: Gloss improvement is not recognized or decreased compared to the control.
[0091] [d]吐出適正 [0091] [d] Discharge appropriateness
前記プリンターを使い、水性コーティング液を用いて光沢紙へ連続で 10枚ベタ印 字を行い、各紙に吐出された（付着した)インク重量を測定し、また、各紙の印字の力 スレをチェックし、以下の基準に基づき評価した。  Using the printer, make 10 solid prints on glossy paper continuously using an aqueous coating solution, measure the weight of ink ejected (attached) to each paper, and check the printing power thread on each paper. Evaluation was made based on the following criteria.
◎:インクの吐出重量のばらつき、印字のカスレが認められない。  (Double-circle): The dispersion | variation in the discharge weight of an ink and the blur of printing are not recognized.
〇：インクの吐出重量のばらつき、印字のカスレが僅かに認められる。  A: Variation in ink ejection weight and slight blurring of printing are recognized.
△:インクの吐出重量のばらつき、印字のカスレがある程度認められる。  Δ: Variation in ink discharge weight and printing blur are recognized to some extent.
X：インクの吐出重量のばらつき、印字のカスレが明らかに認められる。  X: Dispersion of ink discharge weight and printing blur are clearly recognized.
[0092] [表 1] y^T^A1:ァV1Ar〜
Figure imgf000022_0001
[0092] [Table 1] y ^ T ^ A1: V1Ar ~
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000022_0002
Figure imgf000023_0001
Figure imgf000023_0001
〔〕0094[] 0094
y^ Aプ^ V HEMA 2VロH〜—,, 嫘y^： MAA [0095] 表 1及び表 2に示すように、実施例の水性コーティング液は比較例の水性コーティ ング液に比べて良好な結果が得られた。即ち良好なインクジェット吐出適性を有し、 耐擦過性、耐水性、光沢に優れた膜を形成することができた。 y ^ A pu ^ V HEMA 2V ro H ~ ,, 嫘 y ^: MAA [0095] As shown in Tables 1 and 2, the aqueous coating liquids of the examples had better results than the aqueous coating liquids of the comparative examples. In other words, it was possible to form a film having good ink jet discharge suitability and excellent scratch resistance, water resistance and gloss.
産業上の利用可能性  Industrial applicability
[0096] 本発明のグラフト共重合体からなる水性コーティング剤は、インクジェット記録物表 面に耐擦過性、耐水性、光沢に優れた膜を形成し、さらにインクジェット吐出適性が 良好であるためにインクジェット方式によって記録物表面に塗布するコーティング剤と して極めて有用である。また、インクジェット方式において顔料インクとは別に、本発 明のコーティング液を併用することで耐擦過性、耐水性、光沢に優れた印刷物を得る こともできる。特に屋外用のポスターなど長期にわたって鮮明な画像が求められる用 途に有用である。 [0096] The aqueous coating agent comprising the graft copolymer of the present invention forms a film having excellent scratch resistance, water resistance, and gloss on the surface of an ink jet recorded product, and further has good ink jet discharge suitability. It is extremely useful as a coating agent to be applied to the surface of recorded matter depending on the method. In addition, in the ink jet system, a printed matter excellent in scratch resistance, water resistance and gloss can be obtained by using the coating liquid of the present invention in combination with the pigment ink. This is especially useful for applications that require clear images over a long period of time, such as outdoor posters.

Claims

請求の範囲 The scope of the claims
[1] インクジェット方式によって記録媒体に塗布される水性コーティング剤であり、シリコ ーン系側鎖を有し、主鎖にはエチレン性不飽和カルボン酸含有モノマーを必須構成 成分とする共重合体からなる、酸価が 40〜200mg— KOH/g (固形分）であり、重 量平均分子量が 5, 000〜30, 000の範囲にあるグラフト共重合体を含有することを 特徴とする顔料インクジェット用水性コーティング剤。  [1] An aqueous coating agent that is applied to a recording medium by an inkjet method, and has a silicone side chain, and a main chain contains a copolymer containing an ethylenically unsaturated carboxylic acid-containing monomer as an essential component. For a pigment ink jet, characterized by containing a graft copolymer having an acid value of 40 to 200 mg—KOH / g (solid content) and a weight average molecular weight in the range of 5,000 to 30,000 Water-based coating agent.
[2] 上記グラフト共重合体の水酸基価が 30mg— KOH/g以下であることを特徴とする 請求項 1記載の顔料インクジェット用水性コーティング剤。 [2] The aqueous coating agent for pigment ink jet according to claim 1, wherein the graft copolymer has a hydroxyl value of 30 mg-KOH / g or less.
[3] 上記グラフト共重合体のシリコーン系側鎖の重量平均分子量が 3, 000-20, 000 の範囲であることを特徴とする請求項 1または請求項 2に記載の顔料インクジェット用 水性コーティング剤。 [3] The aqueous coating agent for pigment ink jet according to claim 1 or 2, wherein the weight average molecular weight of the silicone side chain of the graft copolymer is in the range of 3,000-20,000. .
[4] 上記グラフト共重合体と共に、さらにエチレン性不飽和カルボン酸含有モノマーを 必須構成成分とするガラス転移温度 (Tg)が 10〜 100°Cの範囲にある直鎖状共重合 体を含有することを特徴とする請求項 1〜3のいずれかに記載の顔料インクジェット用 水性コーティング剤。  [4] A linear copolymer having a glass transition temperature (Tg) in the range of 10 to 100 ° C. containing an ethylenically unsaturated carboxylic acid-containing monomer as an essential constituent, in addition to the graft copolymer. The aqueous coating agent for pigment ink jet according to any one of claims 1 to 3.
[5] インクジェット方式において、顔料インクとは別のタンクに充填され、別ノズルから吐 出され記録物に塗布されることを特徴とする請求項 1〜4のいずれかに記載の水性コ 一ティング剤を含む顔料インクジェット用水性コーティング液。  [5] The water-based coating according to any one of claims 1 to 4, wherein the ink-jet system is filled in a tank separate from the pigment ink, discharged from a separate nozzle, and applied to a recorded matter. An aqueous coating liquid for pigment ink jet containing an agent.
[6] インクジェット方式がサーマルジェット方式であることを特徴とする請求項 1〜4のい ずれかに記載の顔料インクジェット用水性コーティング剤。 [6] The aqueous coating agent for pigment ink jet according to any one of claims 1 to 4, wherein the ink jet method is a thermal jet method.
[7] インクジェット方式がサーマルジエツト方式であることを特徴とする請求項 5記載の顔 料インクジェット用水性コーティング液。 [7] The aqueous coating liquid for a pigment inkjet according to claim 5, wherein the inkjet system is a thermal jet system.
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KR20090060411A (en) 2009-06-12
EP2075138A4 (en) 2011-07-20
KR101385824B1 (en) 2014-04-17
EP2075138A1 (en) 2009-07-01
JP4780196B2 (en) 2011-09-28
US20100068386A1 (en) 2010-03-18

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